Besides Apostrophe I highly recomend Joe's Garage and of course the semi greatest hits album Strictly Commercial. Bongo Fury has a special place for me as well, but it is not the best Zappa album, though it does contain the hilarious Muffin Man. Some people... some people prefer cupcakes better. But I for one care less for them!
Anything by Zappa is good, but check out the Yellow Shark, it is the orchestral work he did and it is bizzare but fantastic. Also Weasels ripped my flesh is a good one.
Zappa's best albums are Freak Out, We're Only In It for the Money, Uncle Meat, Hot Rats, Over-Night Sensation and Apostrophe. Really, if you pick anything from that list you can't go wrong. However, as an introduction I'd say Apostrophe is the ideal choice.
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