I have drove both the Cayman and Cayman S. For me, there was a big difference. The acceleration was slow in the base Cayman. Don't get me wrong, its nimble, solid feeling and a well put together car. It just too underpowered. It didn't feel much stronger than an EX V6 Honda Accord. The Cayman S on the other hand felt great. Good power and nice balance. It also had the ceramic composite brakes. But optioned out it was 70K +.
The base Cayman I drove was priced around 58K. Way too much for what you are getting, IMHO; however, if you aren't too concerned with power, the base Cayman is still a great car. I just think you get a lot more car for less money with the 335i.
Good luck with your purchase.