Lol Mike & Molly? nothing like Chuck. I've seen nearly all of the episodes, only seen half of the new season though, need to get the rest.
As for tv shows that are similar? Well it's storyline is highly unique, but maybe try Burn Notice? It's about a spy who was recently burnt (removed from the field), it's very entertaining, if you haven't heard of it or seen it before maybe just give the first episode a go? I'm not sure on it's label but it's definitely entertaining, one of my favourite shows, I download every episode week by week. (pity their off the air though, for the moment..)