Code-First gives you the opportunity to develop rich domain model which is not entirely affected by the database and EF. That is the principal benefit of starting with code.
It is generally possible to fit the model into existing database. That asks for a bit of imagination and compromises here and there.
Database-First approach tends to make too many compromises that are ruining the domain model. This often leads to so-called anemic domain model, where most of the domain logic gets pushed into controllers. This in turn significantly reduces use of objects in the solution, leading to lack of flexibility and to tight coupling.
Bottom line is that in my projects I prefer Code-First. This is because I am an object-oriented programmer and that gives me the opportunity to develop proper object-oriented application.