It would be a rather boring podcast if you just did play-by-plays of a game. However, if you covered things like:
Paizo News/Upcoming releases
Card previews
Interviews with the Devs
Reviews of Accessories/Miniatures/Mats/Box Additions
Class discussion/strategies
Individual card ratings & combos
Organized Play/Metagame
RPG Background of scenarios & adventures
Q&A from listeners on rules questions
There's probably enough there for a podcast every two weeks, and definitely enough for one a month.
If you're setting one up give me a shout, I'd be happy to help.