I recently decided to go back and listen to all of the episodes of the Writing Excuses podcast. First, the background, then my analysis.
Writing Excuses is a panel discussion on issues related to writing by Brandon Sanderson (fantasy), Howard Taylor (webcomics), Dan Wells (horror), and, starting in Season Six (iirc), Mary Robinette Kowal (fantasy, sf, and puppetry).
Each episode is about 15 minutes long and they frequently have other guests to discuss other issues. They do everything from live shows with random questions from the audience (most random question: "Would you like a bagel?") and very focused issue episodes: What is first-person narration? What is cyberpunk? How do you write a query letter?
I started listening sometime in Season Five, so this is my first time listening to some of the early episodes. And there's some roughness there which are smoothed out in later seasons; for instance, they first tried to hum "shilling" music when one of them was mentioning his own work. In later episodes, they more simply just explain how they did what they do, which is what we come for if we want to hear people with experience in the field.
There are many interesting episodes, but I don't know if I can suggest marathoning as I did to catch up. Rather, since there are 259 episodes, it's probably better to pick and choose and concentrate on those episodes that offer the most help for your particular issue at a particular time.
So, if you have trouble with structure, just go to the website and find episodes about structure. If you want some help with character, look at the character posts. (It's also very nice that a dedicated fan has been writing down transcripts of each episode, and his use of tags might be superior.) If you're interested in a career as a writer, Writing Excuses probably has something for you; and if you're just interested in one or two topics, it's relatively easy to dip in for an episode or two (though they do have running jokes and other callbacks, especially easy since they appear to record many episodes all at once).