Here is a great document on HOW they assign tee times:
http://www.golfthevillages.com/golf-in-the-villages/GolfingIntheVillages.pdf
I am 99.75876% sure you cannot make two tee time
REQUESTS for the same day.
You can however
RESERVE a second tee time within the 3-day window as long as it does not overlap your first one.
As an example, put in
REQUEST for Bogart and Bacall between 11 AM and 1PM, System assigns you Bacall at 11:45. At this point you can now go make a
RESERVATION for second tee time at Bogart at 2 PM.
Hope that make sense.