First of all, have you tried the skinned interface rather than the simple wxWidgets one?
Second of all, when you are watching a video, do you look at the video player's interface, or are you watching the video?
The best thing about VLC is its ability to take a video stream from almost any source and send it to almost any destination. Other projects make players. Other project make transcoders. Other projects make network video streamers. VLC will do it all.
So sure, a presentable interface is nice. But (and with no offense) the absolute last thing I would like to see development time spent on is eye candy. The eye candy can come later.