I listen to the Freakonomics podcast and have done for ages - it's consistently excellent; I also like More or Less off of Radio 4.

As a massive movie fan, I was deeply disappointed with the Empire podcast; it's like listening to 3 slightly drunk people who are convinced of their own hilariousness talking in a pub - fun for them, but grating for everyone else.

I hear that Greatest Events in Sporting History is pretty good, now that I have the shameless plug out of the way I will give you some advice.
The BBC are pretty good resource for podcasts since they put out quite a lot of their shows out in podcast form, meaning there is a large selection of very well produced shows, just a case of finding a topic.
It really is a case of searching for your own interests, reading the reviews and taking a chance, there are a whole load of podcasts that I have only ever listened to one show of.
If you list some of your interests here, maybe people point you in the right direction

As people have said it depends on your interests, I get the Kermode film review and Martin Lewis podcasts from 5Live

Just working my way through the desert island discs archive.

Thanks for the suggestion - such a good call, I'm sitting here painting tonight with one desk lamp on listening to Dawn French on DiD, really good stuff.