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As was already stated, the Vita can play PSP and PSX games so long as they've got digital versions and the 3DS can play all DS games.

When it comes to exclusives, the 3DS has the Vita beat in quality. SMT4, Devil Summoner Soul Hackers, Bravely Default, Fire Emblem, Etrian Odyssey 4, Etrian Odyssey remake, Heroes of Ruin, and Bravely Default are good. Soul Hackers isn't exactly exclusive, but it is in the US. For the Vita when it comes to exclusive RPGs, there's Ys Memories of Celceta which is a good action RPG and Curse of the Curry God which is a rogue like RPG game.  I haven't played the rogue like, but very rarely do rogue like games suck.

When it comes to quality whether it's ports and backwards compatibility, then the Vita takes it.

The 3DS can play all DS games, so you've got Contact, Chrono Trigger, Dragon Ball Z Attack of the Saiyans, Dragon Quest series, Final Fantasy series, Fire Emblem, Front Mission, Golden Sun, SMT Strange Journey, Suikoden Tierkreis, Retro Game Challenge(a good old school RPG and good non RPG games,) and others.

The Vita has Vita games like Persona 4 Dragon's Crown,and the Atelier series, then it's got the PSP and PSX library. These are PSP games I'd recommend that can be downloaded directly from the PSN store. Crimson Gem Saga, Final Fantasy 4 Complete Collection, Growlanser Wayfarer of Time, Half Minute Hero, Persona series(under SMT,) Sega Genesis Collection(Phantasy Star 2-4, Sword of Vermillion, and a lot of good non RPGs,) Untold Legends series, Wild ARMs XF, Yggdra Union, and Ys series.

Here are the PSX games I'd recommend that can be downloaded. Persona 2 EP(sequel of the PSP game,) Square Enix games, Vanguard Bandits, Breath of Fire 4, Grandia, Arc the Lad 1, 2, 3, Arc Arena, Wild ARMs 1, and Wild ARMs 2.