After arriving in White Orchard and heading to the inn, speak with Aldert Geert. Accept his challenge for a game of Gwent, and beat him however you like. Beating him with earn you the "Zoltan Chivay" card. Add that to your deck via the pause menu, and then challenge him for another game. This time, play all of your cards except "Zoltan Chivay" in the first round. He will do the same in response, allowing you to win the next round by just playing "Zoltan Chivay", earning you the trophy.