I'm trying to do the same thing actually. I also have a Rails application, using the Devise Authentication Gem that I would like to create an iPhone App for. I don't know if I have a good answer for you yet, but here's some things I've learned along the way...
According to the README on the Devise GitHub page, it seems that Devise is implementing RESTful authentication with these 2 modules:
Database Authenticatable:
encrypts and stores a password in the database
to validate the authenticity of an
user while signing in. The
authentication can be done both
through POST requests or HTTP Basic
Authentication.
Token Authenticatable:
signs in an user based on an authentication token
(also known as "single access token").
The token can be given both through
query string or HTTP Basic
Authentication.
With HTTP Basic Authentication, your iPhone app won't have to re-authenticate with each request. You will only have to authenticate once, then the framework will remember that it has authenticated.
A few resources that may be helpful for you getting started: