In terms of language, Phoenix is a complete replacement for Rails for me. I feel more comfortable growing a functional codebase, and the BEAM means I don't have to worry about scaling as soon as I would with Rails. I think it's a good fit for when you want to do more with a small, experienced team.
I would reach for Rails when I'm concerned about finding developers (Elixir devs are fewer and more expensive, generally), or if there are Ruby libraries I want that aren't available in Elixir.