There is no button to press. When a player hits you in melee, he burns for 2 seconds, with a 4 second cooldown between two triggers.
The Magma does not win a fight on its own: it makes the fight expensive. Against an opponent who spams clicks and never breaks off, the burns stack up and force him to drink more often than you do.
It is the most passive kit on the server, and probably the most underrated in group fights.