Pff! Metal Gear and Snake's Revenge on the NES? If your PS3 is compatible with PS2 games, get MGS3: Subsistence. Not only does it have the best Metal Gear Solid game (IMO), but also the first two MSX Metal Gear games.
As for old school for NES, SNES, and N64, you can't go wrong with the Final Fantasy games released for those games, but if you have a Wii, and with Virtual Console, getting anything else would be a waste of time. However, as they have shown no signs of releasing them on the VC yet, get a N64 with an Expansion Pack and get Legend of Zelda: Majora's Mask, and Perfect Dark.
Maxrebo, don't you have Virtual Console? Or haven't you been able to connect your Wii up?
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(No longer a mod)
On sabbatical...