I installed NextGEN and found that the gallery display didn't show nice center-aligned thumbnails and descriptions.
I figured, "Must be a common complaint, I'll Google the answer". Well, it does seem a common complaint, but on some quick searching, I found that there wasn't much in the way of results.
I poked around using Firebug and came up with what works for me.
I am using the NextGEN Default theme, you'll have to find a different (but likely similar) CSS change if you use a different theme.
You can modify the theme css where these settings are, but I was lazy and just put them at the bottom of the css. Remember to save a copy of your modified file somewhere so the changes are not lost when you apply the next NextGEN update!
div.ngg-gallery-thumbnail {float:none;}
a.shutterset_set_2 img {clear:both !important;display:block;margin-left:auto;margin-right:auto;}
Voila! Centering!