I don't know if these suggestions will help this show, or formulate a different D&D show but...
-Length: The episodes do need to be longer. D&D is rather long (hell, it can be fucking infinite), so trying to cram it into a 5min episode is just pointless. PA does have the right idea with episodes at 30min or so. And although that may increase production time and the workload, if you're willing to commit (which I assume you are) then it won't matter. Plus, you can release it once a week or something, something that won't work you to death.
-Team chemistry: People who act and respond to one another can easily draw in an audience. It doesn't mean though that the people have to have similar likes or dislikes (one person could think that killing everything is the solution, whereas another would rather be diplomatic), but rather that they can enact/enforce those attributes without gamebreaking conflict. Gamebreaking means a standstill in gameplay, not arguing. Arguing is eventual and necessary in the growth of characters.
-Spontaneous: People who are creative and imaginative, quick thinkers, this allows the game to grow in unknown branches
-Presentation: I'm not saying that you need to dress up or decorate your room, but whichever why you choose to go, make sure it's enveloping. If you don't have a drawing of a room and just navigate by the pieces, then focus more on the player's dialogue. If the set is elaborate, then focus on it as well as the players.
-Cinematography: This ranges from still cameras, to zooming in/out, getting good shots of the people and the set pieces. Any and everything to do with a camera. We can't enjoy the show if we can't watch it.
-The DM: Without it, there's no story to begin with. Having involving stories helps the players and the people watching. Pull out all the stops, backstab your own players, kill one of them off and have the others try to revive them, trick them, etc. Even if they hate you for it, what're they gonna do? Maybe the DM exclusively offers one of the players advantages if they secretly backstabs their own team. This show's DM is...lacking, he doesn't seem into it or even trying (although he did do voice for the town).
-Interactivity: D&D is a highly malleable medium. Audience's could also be a part of the show, let viewers write their own little side quests that would take about 15-25min, have the community vote on it. Maybe the DM will let the audience in on something that'll happen, and the viewers could vote on different options that the story could take. It's a lot easier to watch a video when you're part of it's development.
-Entertainment: This doesn't necessarily mean comedy. Sure, we all like a good laugh, but if I was to watch people play D&D, I dunno. I'd place higher importance on the actual choices and adventures of the players (which is what the game's about) rather than tailoring it to always be funny (if the two overlap, great, but it shouldn't be a requirement). The main thing here is, IT CANNOT BE BORING. Now, no matter whatever ANYONE makes, someone will love it, and someone will hate it (so don't worry about trying to please everyone).
-Drama: Going back to Entertainment and Team chemistry. A player who argues with his teammates and goes off alone in a dungeon would provide intriguing drama. Will he get in trouble? If so, will the others help him? Could he find something they'd otherwise miss? Drama is the life force of any TV, web show, movie, novel, etc. However, drama shouldn't necessarily be enforced either, which leads to be bastardized creation of something like those "Big Brother" shows on MTV.
I hope I covered everything and helped.
I myself would like to see a web series about D&D. One that's NOT The Guild or PA's podcast (mainly because I can't enjoy D&D if I can't see what's going on. Part of the experience is the players, who you can't fucking see).
So here's hope for not only this show, but any who may follow.
(and yes, you all look like emo/goth kids, but that shouldn't effect my viewing pleasure and it doesn't)
