While both are designed to be re structural, Rolfing is a very deeply penetrating technique that can be intense.
Myofacial release work focuses on using slow holding patterns to pull open facia where adhesion has developed. It tends to be a lot of hold and wait for the release movements.
They are both designed to help restore a natural state and can be used to support each other but are dramatically different to experience. Both have specific situations where they are best applied to.
As for classes in it, check online with the Rolfing institute in Arizona regarding workshops in your area. However, I'd really recommend finding a local practitioner to have a session from first to be sure it's something you'd like to pursue.