I don't point this out usually, but this is usually what I think about before the snap...
1) Personnel - How many WRs, RBs, TEs. Often you can anticipate this based on subbing from the sidelines.
2) Formation - Usually typical, but try to notice balanced vs unbalanced looks, twins, trips, trips to the TE side, TE covered, etc.
3) Backfield alignment - Where is/are the back(s)? Wildcat? Offset or pistol? Etc.
4) Defensive alignment/coverage - How many in the box? Coverage? Most college teams are more complex though, disguising coverages, or playing man on half the field and zone on one half or other mixes. With motion you have a bit of a better idea.
5) Linemen alignments - Usually don't get this far, but pulling offensive linemen often tip themselves off by lining up slightly deeper off the ball to get angles to pull, etc.