Yes, if you include a round trip to Koyasan, the pass usually pays off.Note also that you can use the pass not only on Nankai but on most trains and buses in the greater Osaka region, except JR trains.
Btw, what is Nankai limited express? Is it just another type of express train on some of the routes?
It is a faster category of train, for which you have to pay a small supplement.
so, bascially I can wait for an express train instead on any of the Nankai line. Is it correct?
Yes, just wait for an express train. You can research timetables in advance by using the following website:
http://www.jorudan.co.jp/english/norikae/