As far as games go it really depends on your preferred genre. There's quite a lot of great games available for it now.
Some of my faves in no order:
AAA Games (exclusives)
Uncharted 1-3
inFAMOUS 1 & 2
The Last of Us
LittleBigPlanet 2
Killzone 2
Metal Gear Solid 4 & MGS HD Collection
MotorStorm Apocalypse
Resistance 2
Puppeteer
Ratchet & Clank: A Crack in Time, Tools of Destruction, HD Collection, Into the Nexus
Dead Nation
God of War 3, GOW Origins Collection, GOW HD Collection (1 & 2)
Sly Cooper HD Collection (1-3)
Heavenly Sword
3D Dot Game Heroes
Dragon's Crown
Twisted Metal
PlayStation All*Stars Battle Royale
Sports Champions 2 (if you have the Sony Move motion controller)
Ridge Racer 7 (3D License)
Gran Turismo 6
Indie (exclusives)
Soldner X2: Final Prototype
Rock Band Blitz
Super StarDust HD
PixelJunk Shooter 1 & 2
PixelJunk Monsters Deluxe
Sine Mora
Super Motherload
Shatter
Unfinished Swan
Sound Shapes
Beat Hazard Ultra
Journey
Flower
More favorites
Tomb Raider
Pac-Man Championship DX
GTA V
Limbo
Gatling Gears
Critter Crunch
Bomberman Ultra
Bit.Trip Runner 2
Rock Band 3
DuckTales Remastered
Rayman Origins
Rayman Legends
Doom 3 BFG Edt.
Darksiders II
Portal 2
Child of Eden
Chime Super Deluxe
Pinball Arcade & Zen Pinball (plus a ton of DLC tables!)
Burnout Paradise
Ni No Kuni: Wrath of the White Witch
Batman: Arkham Asylum
Back to the Future (TellTaleGames)
The Walking Dead (TellTaleGames)
Assassin's Creed Revelations
Mass Effect Trilogy
Castle Crashers
Scott Pilgrim Saves the World
Guacamelee
Shoot Many Robots
House of the Dead Overkill
Classics on the PS3
PS1 & PS2 Classics (hundreds to choose from)
Neo•Geo Station (with games available such as Metal Slug 2, KOF 96, Baseball Stars Pro, etc..)
Sega Vintage Collection (Revenge of Shinobi, Super Hang-On, Toejam & Earl, Streets of Rage 2, etc..)
Capcom Arcade Cabinet (Ghosts 'N Goblins, 1942, Black Tiger, etc...)
Daytona USA HD (1080p/60fps)
Afterburner Climax (1080p/60fps)
NiGHTS into Dreams
Crazy Taxi HD
Castle of Illusion HD
Sonic CD (remastered in 1080p 16:9)
Super Street Fighter II HD Remix
Dragon's Lair (HD _ 16:9)
Dragon's Lair II (HD _ 16:9)
Space Ace (HD _ 16:9)
Wolfenstein HD
The Simpsons Arcade
X-Men (6 player version)
Okami HD
R-Type Dimensions
Final Fight: Double Impact
Alien Crush (TG-16 classic)
Another World 20th Anniversary Edition
I should probably stop naming games I like.
I also highly recommend PSN Plus. They give away quite a few free games each month, along with discounts, and 2GB in auto game save storage.