From here
http://ubuntuforums.org/showthread.php?p=4445289sudo apt-get install ubuntu-restricted-extras w32codecs libdvdcss2 mplayer-nogui mozilla-mplayer smplayer
and perhaps
sudo ln -sf /usr/lib/win32 /usr/local/lib/
beyond that I don't know
Google is a wonderful tool, search rmvb files/ubuntu and there are many discussions that might fix your problem.
Cheers and good luck.