Sebastian Freis gave the guests a 1-0 lead early on, but Sami Khedira tied the score in the 22nd minute. Mario Gomez put Stuttgart ahead in the 68th before Ciprian Marica finished off Karlsruhe with a goal in the 87th.
Stuttgart now have 10 points - even with Hoffenheim and Hamburg - to be one point behind leaders Schalke.
Karlsruhe, who were hoping for their first victory in Stuttgart since 1965, remain on three points just outside the relegation zone.
Karlsruhe grabbed the lead after just eight minutes when Alexander Iashvili sent a high cross to the far left post where Freis was all alone to head into the near corner.
But Stuttgart evened things in the 22nd minute as Gomez gathered the ball, ran onto the left wing and crossed into the middle where Khedira headed in the equaliser.
The hosts missed a golden chance to pull ahead after 37 minutes when Cacau found Jan Simak, but his looping header from point-blank range gave Karlsruhe goalkeeper Markus Miller enough time to make the save.
Stuttgart keeper Jens Lehmann was unable to clear a ball seven minutes after the break but Michael Mutzel could not find the target.
Armin Veh's side finally grabbed the lead in the 68th minute when Germany midfielder Thomas Hitzlsperger lofted a pass over the Karlsruhe defence for Gomez, who beat Miller one-on-one to the left corner.
Marica ensured the win in the 87th minute when he beat the off-side trap, and then Miller, to seal the points.
In a game of few clear-cut chances, Unai Emery's men were lacklustre throughout but their persistence paid off when the former Real Madrid winger pounced from eight yards to guide home an excellent lofted ball from David Villa.
Osasuna will feel hard done by as they appeared to have done enough to take a point, despite losing full-back Cesar Azpilicueta to two yellow cards in quick succession early in the second half.
However, their time-wasting antics ensured they were awarded little sympathy by the relieved Mestalla faithful.
In a disappointing first half, Valencia were tentative and showed glimpses of the fragile confidence that plagued them for much of last season.
So it was no great surprise when the game's first real chance fell to the visitors on eight minutes.
Jaroslav Plasil sprang the offside trap to race onto Javier Portillo's exquisite reverse pass and cut the ball back to Hector Font, but the forward could only blaze over when he surely would have scored had he kept the ball down.
However, the hosts did threaten to spring into life on a few occasions without ever delivering the final punch.
Joaquin and Manuel Fernandes worked some space from a corner to find Miguel alone on the edge of the 18-yard box but the full-back suffered a rush of blood and wasted the opportunity with a scuffed shot.
Mata tried his luck from 25 yards on the half-hour mark, his well-struck effort forcing Ricardo to dash across his goalmouth and he will have been relieved to see the ball drift wide of his left-hand upright.
Then Villa drilled a left-footed shot across the face of goal on 42 minutes with Joaquin unable to connect with an outstretched boot at the far post.
A minute later, Mata worked the visiting keeper with a left-footed strike from the edge of the 18-yard box.
In the second period, even half-chances were few and far between following the dismissal of Azpilicueta.
The full-back was given his marching orders for two fouls on Mata in the space of 10 minutes, the second for denying his opponent the opportunity to race into the box for a loose ball when both players were grounded in the corner.
From that point, the play became even more disjointed as the visitors played the clock as best they could, drawing cheap free-kicks out of the Valencia defenders and generally wasting time.
Los Che's chance to win the game appeared to have disappeared with four minutes remaining when Mata hit the base of the post with a fine strike from 15 yards, the ball bouncing back into the danger area but evading a trio of white shirts.
However, the Mestalla crowd didn't have too long to dwell on their apparent misfortune, Mata popping up less than 60 seconds later, latching on to Villa's pass and finishing with aplomb to secure the points.
Following an indifferent first-half performance, De La Red put Madrid into the lead eight minutes after the restart and Van Nistelrooy netted his side's second with 17 minutes remaining to ensure a comfortable win for the champions.
Madrid came into the game under pressure following an indifferent start to the campaign.
Schuster's side lost at Deportivo La Coruna on the opening weekend of the season and were far from convincing in a 4-3 win at home to promoted side Numancia last Saturday.
A 2-0 home success against Belorussian minnows BATE Barisov in the Champions League on Wednesday also failed to silence the critics, but Madrid looked better here.
Gonzalo Higuain almost set up Raul after 10 minutes, but Racing cleared before the Real captain could get a shot in.
And De La Red - a surprise inclusion on the left of midfield - forced Tono into a fine save with a fierce low drive nine minutes later.
The Spain midfielder also saw a long-range effort deflected behind after 32 minutes.
But Madrid switched off at the back as half-time approached and needed a pair of heroic saves from keeper Iker Casillas to deny Jonathan Pereira.
Guti was forced off with an injury just before the break and was replaced by summer signing Rafael van der Vaart.
But it was De La Red who made the breakthrough eight minutes after the interval.
Higuain charged forward on a quick counter-attack and released the former Getafe loanee, who swept the ball home from close-range to give the visitors an important lead.
But Schuster's side struggled to build on that advantage as Racing looked for a way back into the game.
And Mohamed Tchite almost provided a lifeline for the northerners after 69 minutes, but was just off target with his header.
Four minutes later, though, the match was effectively over as a contest as Van Nistelrooy bagged his side's second after evading a couple of challenges and slotting home just inside the post.
It was a typically clinical finish from the Dutchman and gave Madrid an important cushion for the remainder of the match.
Their advantage came under threat after 77 minutes but Tchite's header was cleared off the line by Van der Vaart.
De La Red fired over four minutes from time and Gonzalo Colsa was off target with a free-kick at the other end as the game finished with a flourish.
The points went to Madrid, who moved up to sixth place, where they sit just one point below joint leaders Valencia, Almeria, Villarreal and Espanyol.
Racing, meanwhile, sit just above the drop zone with two points from their three matches.
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