I was hoping to develop a library of the ones I like that I could go to anytime.
That's easy to do. Create a folder in My Documents and/or My Pictures and name it something like GIFS. Paste any smilies you like into that folder and they will be handy when you want to copy and paste into an email or message board. Don't know why it won't animate in Word.
I would strongly advise that you get rid of Smiley Central. When you install it the MyWay toolbar (which they call Speedbar) comes along with it plus other Fun Web Products like Cursor Mania and PopSwatter that you didn't ask for. There are several reasons to get rid of it that I could go into further if you like, but the main point is that it is unnecessary if all you want is the smilies. And the program is invasive and known to cause performance problems. See this page for an example:http://www.nwfusion.com/newsletters/web/2003/1208web2.html
If you want to keep the Smiley Central smilies, go to the MyWay (or whatever it is called) folder in the Program Files directory. Look for a subdirectory that contains the animated GIF's. Copy and paste those into the library you want to make and they'll be there for the asking without having Smiley Cental installed.