I had the reverse idea. A plugin for VLC that takes the MD5SUM of whatever file you're watching and looks for the matching/appropriate subtitle file and autoloads it.
[1] http://smplayer.sourceforge.net/
[2] http://trac.opensubtitles.org/projects/opensubtitles/wiki/Ha...
Having said that I don't mind having to compute 4gb md5's, since that also helps me to check the integrity of the file at a later date.