This sounds like a neat idea and I would definitely check out a few episodes. I've just starting exploring the world of solo RPGs and I'm really enjoying them as a writing exercise, so I can see how this could create an interesting story with all sorts of twists and turns.
I'll echo the above concerns about quality. That's the first thing that kills my listening experience and makes it unlikely I'll bother with a podcast, even if the content is something I enjoy. But I also have no experience with producing a podcast so *shrug* can't offer insight there.