Wait a moment !!!
Are you sure you have the VANS perk ??? -> http://imgur.com/bd7Xiv2
Secondly, just press L1 (for a second) on your PS4 joystick, and you will see something like this: http://imgur.com/BADMIgJ%C2%A0
You have to have your weapon ready and an enemy in sight...then you activate it, pick a body part, hit the attack button as many times is called for then hit the action button to start unloading.
Is mthe VANS really worth the point? Seems pretty pointless to me considering you can place markers on the map and follow the compass.
If you hold down the V.A.T.S key (Q), you can enter V.A.T.S mode without enemies in sight. Useful for V.A.N.S.