Iosue
Legend
Aw man, I think the Penny Arcade / PVP players are generally fantastic. I loved listening to them as Mike learned to play D&D for the first time, and Gerry is just a brilliant and interesting guy. If you're looking for a place to start, start with their first series, and try to listen/watch in chronological order; even though it's 4e.
Based on my relisten of the first season (recapped here!), I would suggest skipping the first season entirely. Only half of it is Chris Perkins, and he absolutely not on his game in them. The PA guys and Kurtz are still feeling out their characters. I would recommend Season 2, or even better yet, Season 3. The first chapter of Season 3 is like Edward Norton's poker speech in Rounders: it makes me want to play some D&D!