I finally got around to listening to the first few Penny Arcade/PvP D&D podcast sessions. Series 1 is a basic primer on 4e and was super fun. It then gets even better when Wil Wheaton joins the party for Series 2 & 3, and they actually do some role-playing.
I also didn't know how to manually add a podcast subscription to iTunes, so these instructions were handy...
- From the dropdown menus, select Advanced --- Subscribe to Podcast
- When prompted for a URL, enter http://www.wizards.com/dnd/rsspodcast.xml and click OK.