As the ball approaches the player with his back to goal, click R3.
Said player will then flick the ball up.
Move directional stick towards goal and the player will rainbow it over his, and often the defenders, head.
Volley the ball as it drops back to your player.
There is a training exercise on it, and I think only certain players can do it.
This is very useful I find with free kicks just inside the opponents half.