Seems like some of these suggestions have problems of their own attached. Matt's leave with L2+R2 (no shot input) suggestion seems the most do-able. It seems reasonable to have a sudden late reaction of squeezing in those two.
I keep saying it, but the crazy thing right now on PS4 is, that it's attached to either L3 or R3, or X. That's a lot of "leave" options. Also, controllers age and as they do and slacken, L3 and R3 become much easier to do. I thought I'd gotten on top of the situation (when I had a new PS4 controller), but it's starting to become easier to happen again.
As for someones suggestion about having unorthodox shots be moved to face buttons because of their more pre-meditated nature? In theory that sounds fine, in practice it's very hard to push the LAS and RAS where you want to push anything other than the trigger buttons up top. The face buttons are generally thumb-operated and that's hard to do when the right thumb is taken up with the RAS.
Again, personally I feel it's just about giving the player more optional set ups, i.e. an option that offers the player something like: "Leave button: Right Stick / Left Stick / 'A' / RB+LB / RT+LT / RB / LB"
Personally using the face buttons then inputting something on the controller isn't something difficult in the slightest. I'd suggest giving it a try in the nets just to see how it feels (even though it does nothing right now, unless you hit 'A' or 'X' depending on console), it is remarkably simple to do, doesn't take very long, just that split second extra premeditation (which you need for unorthodox shots anyhow). Just to clarify, it would operate like sticky keys, you press it some time in the run up, and the modifier is on for the duration of that ball.
The difference for leaving though is it needs to be an instant reaction. You need to be able to be able to just do it reflexively, and I don't find any of the options particularly good for that at the moment. So again, keep the options they currently have, but offer other set ups, maybe even the ability to fiddle with set ups a bit. More options will only serve to make the game better.
Equally if the face buttons system worked well, you could actually offer up to three, even four different types of unorthodox shots using those buttons as modifiers (up to 7 if they can work together, even more if you can modify the modified shots with the triggers). But that is a bit trickier as it would require it to be a default control, which defeats the purpose of my entire suggestion. Not every player is going to like the same set up.