I agree with SNS22. Very is my favorite PSB album. I can see why some people getting into PSB may not buy Very because, like SNS22 said, it doesn't have the big hits like West End Girls or Opportunities. Still, Very is a solid album all the way through.
Again, I agree with SNS22 and j0wled about Alternative. I think that PSB are one of the best b-side bands out there. Other than a few bad b-sides like If Love Were All, The Sound of the Atom Splitting, What Keeps Mankind Alive, or Euroboy, the rest of the songs is awesome. I especially love In The Night, Jack The Lad, Don Juan, Miserabilism, Hey, Headmaster, One of the Crowd (Chris Lowe with vocoded vocals), and Your Funny Uncle.
However, I also love Bilingual, Nightlife, and Release (Johnny Marr plays the guitar on seven songs for Release), but Release isn't your typical PSB's album. As you can tell with Marr playing on seven songs, it's more of a guitar-oriented album with some decent electro tracks like Home & Dry, The Samurai in Autumn (killer synths), and Here (very cool synth song).
Even Fundamental, their latest album, is PSB going back in time.
However, if you want that classic PSB sound, then go with Please to Very, as j0wled suggest.