Tonight's the Night is the only Neil Young album I'd recommend. Fuck Neil Young.
From what I know of you, Thumbtack, here's some Aphex starting points:
Richard D. James Album is probably his most accessible, and has a louder, more aggressive tone.
If you do get that one, the next one you should get is the Come to Daddy LP, which is similar, but a bit lighter and weirder, and then I Care Because You Do, which is where, in my opinion, he best balanced commercial sensibility with... everything else he does.
If you would rather dive right into his best work without a preparation course, get both volumes of Selected Ambient Works, but be warned that he's serious about the ambient part, especially on Vol. 2, and 26 Mixes For Cash, which is titled similarly to Throbbing Gristle albums. He'll do a remix without ever having heard the original song, for example. It's not easily described, but you have to hear it.
Don't get drukqs until you're pretty familiar with his work, but once you kind of understand him, it's a must.
And get that Mike and Rich album, and the Windowlicker single for light, funny stuff, which is insanely disturbing at the same time.