one definition of toss is: jerk (one's head or hair) sharply backward: Paula pursed her lips and tossed her head.
Does that mean she pulled / fixed her hair backwards?, e.g., to make pony tail.
No. It means to physically move your head quickly in a backward direction. Think of it as having a rock in your hand. You can throw (or toss) the rock forward or you can toss it behind you. The way I read your sentence is that she moved her head backward since there is no other indication as to direction and the usual meaning in this case is to move your head quickly backward.
Why is the meaning of such gesture? (Toss your head backwards).
It could be flirtatious. Or it could just be that her hair was in her face and she wanted to move it.