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I'd suggest various films. Kiki's Delivery Service, Millennium Actress, Grave of the Fireflies, Ghost in the Shell, The Ideon: Be Invoked, Night on the Galactic Railroad, Adolescence of Utena and probably others like those by Shinkai.
As for series the obvious ones with good dubbing like GITS, Bebop, FLCL, Haibane Renmei, Beck and Freedom. Brotherhood, Monster and perhaps comedy things like Nichijou would be good as well.
Clannad has too many ''cute'' girls and those pretty awful character designs, I am a fan of the show but my mind had already been warped before watching. First time anime watchers should watch something a little ''classy''.