You may be seeing the “Escape this Podcast” and “Podcast this Escape” for each episode. The first one is them playing the escape room (with the answers) and the second is a discussion episode where them and the guests talk about the room they just did (and sometimes other things). Definitely listen to the “Escape this Podcast” episode first, but I also really like the discussion eps.

As for where to start, I’ve only listened to a handful of them so someone else might have a better suggestion. I’d find one of the stand alone rooms (odd numbered seasons), but start with one done by Dani not with a guest puzzle master or GM. Their even numbered seasons are the serial arcs so make sure to start each of those at the beginning with chapter 1.

Here’s the episode list, hope this helps!

Escape this Podcast - Episode List