If you're more comfortable working with databases first, I would go down that route. This question has a lot of pros/cons for each.
I've recently used code first for a project and I regret that decision. Although it is incredibly powerful, it was an unnecessary learning curve and ultimately took far too long to setup a simple schema.
If you want to learn how code first works, and time isn't an issue, then you may as well go for it. Else, what do you really have to gain from it?
Ultimately though, if you're developing it and you already have a sufficient skill set in one of these, use it.