I'm a BDDer, so I tend to do outside-in. At a high level that means establishing the project vision first (you'd be amazed how few companies actually do this), identifying other stakeholders and their goals (legal, architecture, etc.) then breaking things down into feature sets, features and stories. A story is the smallest usable piece of code on which we can get feedback, and it may be associated with one or more scenarios. This is what Chris Matts calls "feature injection" - creating features because they are needed to support stakeholder goals and the project vision. I wrote an article about this a while back. I justify this because regardless of how good or well-tested your code is, it won't matter if it's the wrong code in the first place.
Once we have the story and scenarios, I tend to write the UI first, followed by the classes which support it. I wrote a blog post about a real-life example here - we were programming in Java so you might have to do things a bit differently with Rails, but the principles remain. I tend to start writing unit tests when there's actually behaviour to describe - that is, a class behaves differently depending on its context, on what has already happened before. Normally the first class will indeed be the controller, which I tend to populate with static data just to get the UI into shape. I'll write the first unit tests to help me get rid of that static data.
Doing the UI first lets me get feedback from stakeholders early, since it's the UI that the users will be interacting with. I then start with the "happy path" - the thing which lets the users do the most valuable thing - followed by the exceptional cases, validation, etc.
Then I do my best to persuade my PM to let us release our code early, because it's only when the users actually get hold of it to play with that you find out what you really did wrong.