Hello, I am wondering which route gives one a higher chance of being selected for pilot training: USAFA or ROTC?

USAFA, if there are less pilot spots then they will be taken from USAFA before they choose from ROTC.  I think this year's graduating class had 500 of the first-classmen go to pilot training, not all will fly fighters mind you, out of the 1,000 or so graduating first-classmen. In summation, definitely USAFA.

By the way, would I really have a better shot at flying with the Navy than the Air Force?  I can think of many reasons why this would be true, but I'm not sure.