Haiku will have multi-user support sometime. It will be easy to understand and you will be able to ignore it (like single user) if you want. The most recent discussion from the Haiku developers is here:
http://www.freelists.org/post/haiku-development/Multiuser-is-a-mistake
The GUI is connected to Haiku so you can't change it. See:
http://www.haiku-os.org/docs/userguide/en/gui.html
But you can change the "decor" to, for example, make it look like Wondows or Mac OS X. Very few extra decors exist at the moment, as far as I know.