There are two types of Head-to-Head modes, one can be chosen within the 'Casual Games' settings, and the other is one of two 'Ranked Games' modes.
I won mine by playing the Ranked Head-to-Head, and am not certain if you can achieve this trophy through the casual gameplay. Players tended to be overly aggressive, for the most part, so just lay an All-In at the right time when you have the pot lead, you'll then win the tournament and the trophy will be yours!