MGS4 is a must, if you do not own this game then you don't deserve to have your ps3 and should hand yourself in for termination at your nearest playstation outlet......
ahem.
Moving on there's a wealth of games available for the PS3, however, there aren't actually that many that make full use of the technical capabilities of the console since a lot of multiformat games are direct ports so they look a bit too moneybox360.
However, I would advise these for an all round taste of the many facets of the ps3 gaming experience:
1.MGS 4; Graphically it is amazing, even now, many ps3 games don't meet the mark when comparing graphics to the game. The game itself is huge and as you can expect the plot is diverse and surprising. The play system is very simple and smooth, it eliminates MGS3s camochange system for the fluid octocamo system (though I actually liked MGS3s system more tbh). Finally it's MGS4. You find out the end of the story. And besides it's worth playing just to see Raiden finally become more than a metrosexual ladyboy, in fact he is downright badass in this game.
2.Mirrors Edge; Mirrors edge was the second game I ever bought for my PS3. It has a unique first person freerunning playstyle that is easy to get to grips with, yet hard to master. The game oozes sexy visuals. If you want to see the PS3s lighting effects and awesome visuals then this is the game to get. The game itself however is every short, but the levels and online leaderboards lend some replayability to it. Besides, it's just ubercool. Awesome graphics backed up with a great sound track and easy to play. Just get it ;)
3.Fallout 3; Basically this was what everyone wanted in Elder Scrolls: Oblivion. Guns. This game is massive. It's a first person RPG/Shootemup with the good old choose your destiny principle built right into it. A massive land with loads to do will keep you occupied for hours on end. And now with the advent of the game of the year edition there's even more to do.
4.Resident Evil 5; This game is just great, full stop. The playstyle from resident evil 4 has been refined and tweaked to create a smooth combat oriented resident evil, while still maintaining the sheer terror you feel as the prey against swarms of mutated and disgusting creations. However in this game you're not alone, you have a partner and she is vital to your survival (unlike certain daughters of presidents I dare not mention). The AI in this game is superb. Your partner is as flexible and fight worthy as you the player and there are certain points in the game where she is a vital asset. The game itself is beautiful visually. The attention to detail is remarkable and the animations for the characters are very believable. Besides, everyone wants another go at Wesker after Code Veronica don't they?
5.Disgaea 3; One for the hardcore RPG fan is this. Disgaea 3 plunges you into the most ridiculous story yet in the Makai universe. With a wealth of new characters as well as old this game is both entertaining and engaging. It maintains the standard simple graphics format with the giant chess style gameplay. Along with a wealth of bonus material and probably the biggest list of DLC content on PSN. An easy game to play, a hard and time consuming game to masterand and an even harder and more time consuming game to get a team of lvl 9999 chars with ultimate weaponry..... ahem. Just get it it's great :P
So anyways that's probably what I would say are the top 5 must haves. There's loads of others but for me those are probably some of the staple bread and butter of the ps3 market.