Try to get the VGA cable if you can...and then get a converter to component. The DC library is 480p. Yeah, way ahead of it's time.
Second, the Resident Evil titles...RE 2, RE 3, and RE Code Veronica are fantastic. The RE ports are the best versions out there. They beat the GC version, because everything is already unlocked. That's a huge plus.
Umm, I recommend Shenmue 1, Jet Grind Radio, Skies of Arcadia, Sonic Adventure 1, Soul Calibur, Power Stone 1 & 2(you'll be pissed they didn't continue it), Marvel Vs Capcom 1 & 2, and Toy Commander.
There's some others but I'm having a hard time remembering them. There was some high quality stuff released for the DC.