OK, so I just got this and it feels like it has to be a certain type of situation for your player to perform a toe poke.
I put in a cross for Falcao and when the goalie came out to challenge I pressed
and
for my shot and Falcao hit it with his toe over the keeper. You may want to try by just pressing your shoot button if it doesn't work while holding
.
To do a Toe Poke you need to have the goalie coming out to challenge you when you are 1 on 1 as I have only seen this shot once since I started playing. I have included a video of how the shot looks and how the keeper was coming at me. Hope it helps a little.
Let me know if you find another way to get this and I can update the solution.
**EDIT - Thanks to Skepta11. You could also try to hit
and your shoot button.
**EDIT - I just scored another Toe Poke. I uploaded a second video showing that. But for the second video I actually took the shot using
and
(or whatever your shoot button is). I think the shot has to be done when the keeper is going down to block you.
**EDIT - See DrSchmock's comment, he has another way of getting this as well if the above options aren't working.