Check out this thread for great recommendations: Dining and lodging in Piemonte, Portovenere, Florence, Bologna, Venice, Verona, and Lake Garda
We loved Cappun Magru in Manarola for lunch. I believe they sell wine by the bottle, all local. Cinque Terre whites are really interesting, highly mineral-driven wines that match the local seafood brilliantly. (I did not try any reds.) There is also a wine shop toward the bottom part of Manarola that also carries many local wines.