Im running vB 2.3.2..how would I make it so my smilies are in a certain order..

I am afraid this is only done with a hack.
vBulletin 2 hacks are on vBulletin.org and free for download to licensed members. Search for smilies or smiley or order Hopefully you find what you are looking for.

Alright, I wasnt sure if it was a hack or not.

Hmm i've been wanting something like this, hopefully it comes out for vB3. :)

It is default in vb3.
In vBulletin version 3 you can categorise smilies and set their display order.
Just check the smilie manager in the admin control panel.