I like VLC when watching a DVD rip that needs subtitles, but what I realy hate with VLC is it does not remember where you last stopped watching. As I have a few work related training videos I like to watch (when Im really bored) and stop and start over a few days I use KMPLAYER which just starts where you last stopped watching.
Oh, and if you want something for music as well, WINAMP is good as an iTunes replacement as it allows you to copy music to your PC from an iPod which iTunes doesnt allow.
For easy loading of lots of free programs try a site called NINITE, it will load all the software you select without you getting the bloatware that is sometimes loaded if you dont deselect the check boxes. It has all the top free utilities you may need.