The Wailing Ultimate was also massive for me, really kick-started an appreciation of music outside of the UK.
Other choice primers include:
In Love With These Times - Flying Nun comp, including the fantastic Straitjacket Fits: http://www.discogs.com/Various-In-Love-With-These-Times/master/21548
Just Say Yeah - potentially unfashionable, but actually rather good, post-goth/grebo comp. GBOA, Crazyhead and Bomb Party are all present and incorrect: http://www.discogs.com/Various-Just-Say-Yeah/release/893668
Downer Rock Genocide - great title, loads of gnarly old UK rock nuggets: http://www.discogs.com/Various-Downer-Rock-Genocide/release/1277608
Speaking My Mind: lots of hard psych/prog niceness (tons of these type of comps around, but this is the best, and toughest, I've heard): http://www.discogs.com/Various-Speaking-My-Mind-New-Rubble-Volume-2/release/1518251
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