Be sure to grab all of the Halloween shows. ESPECIALLY White Album ('94) and Remain In Light ('96). Also, no collection is complete without the epic Live Phish 11.
I’m also quite a fan of 1991.7.21, Arrowhead Ranch. It’s the best example of a Horn Show out there (aside from 10.31.96), and is actually much better than the Live Phish one (19, I think). It’s performed a LOT better, the sound quality is superior, Mike’s bass doesn’t sound awful, and Page’s keys aren’t as fake-sounding (think Colorado '88). No cuts to audience source, no mysterious clicking and noise, better setlist… premium early Phish.
I also reccomend Colorado '88; I know it isn’t technically a show, but if you can get used to Page’s cheesy synth-piano it’s an amazing document of a smaller, more intimate, chilled out Phish. Be sure you get the bonus-tracks-having version, since those are amazing.
Oh, and try to check out the 1984 Nectar’s gig, if you can find it. The sound is a bit muddy, but it’s a polar opposite of late Phish. No keyboards, a bunch of silly covers, the Dude Of Life singing a faster version of Fluffhead with different lyrics, a ten-minute drum solo, and a Slave that will catch you totally off-guard (no keys!)