The tall England striker's goal deservedly secured the Shield outright for the 10th time - with five more shared - for Liverpool, who had gone ahead in the ninth minute with a 25 metre John-Arne Riise shot and looked far more together than the Londoners.
The one bright spot for Chelsea was a confident performance by 30 million pound ($56.9 million) striker Andriy Shevchenko, who equalised in the 43rd minute with a typically predatory goal and looked comfortably at home in his new environment after his close-season move from AC Milan.
It was not such an auspicious start for Chelsea's other big-name arrival, however, as Germany captain Michael Ballack earned the first booking of the game and limped off with a hip problem midway through the first half.
Sunday's game, the prelude the next weekend's start of the Premier League season, failed to capture the imagination of the Chelsea fans and there were swathes of empty seats as only 56,275 filed into the 74,000 capacity stadium.
The absentees seemed to have made a wise choice as Liverpool, with last week's Champions League qualifier against Maccabi Haifa already under their belts, unsurprisingly looked the more settled side.
LOW SHOT
They blasted into the lead when left back Riise collected the ball inside his own penalty area, advanced unopposed down the right deep into Chelsea territory before unleashing a powerful low shot that somehow found a way past goalkeeper Carlo Cudicini,
Mohamed Sissoko outshone Ballack in midfield as Liverpool dominated the first half but they ended it level after Frank Lampard chipped an inch-perfect 30-metre pass for Shevchenko to chest the ball down on the run before expertly steering it beyond Jose Reina.
Shevchenko looked sharper than he did during the World Cup for Ukraine when he struggled for fitness after a knee injury but few of his new team mates could claim the same.
Chelsea coach Jose Mourinho lamented the fact that so few of his squad were match-fit and did his best to sharpen up as many as possible with regular substitutions. With Benitez also using his full allocation of five changes, the second half was never able to settle into any rhythm.
However, one of those substitutes was Liverpool's livewire forward Bellamy and he created the winner when he skipped down the left wing and crossed for Crouch, inexplicably left unmarked in front of goal.
Liverpool's fans, who used to treat this fixture as a mere sideshow to their regular league title wins, greeted the victory as if they had won the Champions League again but they know a far more significant meeting will come in the league at Stamford Bridge on Sept 16.
Before that, Liverpool will get the new Premier League season underway next Saturday when they visit promoted Sheffield United while Chelsea start on Sunday at home to Manchester City.
However, both coaches will have little chance to work with their players this week as most of them will be involved with their national squads for Wednesday night's extensive programme of friendlies.