The Hamburg midfielder took just three minutes to get the visitors off the mark, latching on to a neat through ball from Wesley Sneijder to bury it inside the far post.
The Thais were overwhelmed throughout the game and did little to trouble the Dutch.
They soaked up constant pressure until the 41st minute when John Heitinga added a second for the Dutch, climbing high above the Thai defence to head home Sneijder's corner from the left.
The Dutch continued to press the hosts and got their third on 55 minutes when Dirk Kuyt found the unmarked Jan Vennegoor of Hesselink, who lifted the ball into the top corner from close range.
Tawan Sripan salvaged some pride for Thailand on 65 minutes with a sweetly-struck free kick from 25 metres.
The Netherlands beat South Korea 2-0 last Saturday, with Van der Vaart scoring both goals.