"La Mala Educacion" is brilliant, proving that Almodovar is head and shoulders above any spanish director out there, and any american director, for that matter... If you have the time, listen to Almodovar's commentary, too.
If you want to listen to spanish as it is spoken in spain (as opposed to mexican spanish) watch every movie of his. also - Atame(tie me up/tie me down), Tacones Lejanos(high heels), Law of desire, and Matador. Wonderful movies, great scripts.