The reason it is still fun after 20+ hours of play is because of the skill and gear progression that comes with most builds in the game. 95% of builds on PoE scale with special uniques or powerful rares as well as getting gear that has more linked sockets (5 socketed and linked sockets on gear are a lot more rare than 4 linked gear, and 6 linked gear  extremely rare and endgame to acheive in most cases). Both of these will change will change how the skill works/increase their damage output significantly, making you want to progress even more to see how far you can take a build idea.

So the long and short of it is yes in it's most basic form the fun of playing the same skill over a long period is to see the returns of your investment into the skill and seeing how far you can take it, which is much more rewarding than it sounds due to the sheer complexity and number of options the game has to offer.