Pliskova claimed a 6-2 7-6(4) 7-5 victory in the white group in two-and-a-half hours.
The 24-year-old stormed out of the blocks as she went 4-1 up in the first set with an early double break, while Muguruza struggled to impose her game on the court.
The Spaniard showed some fightback when she saved two set points, but it was not enough to halt Pliskova as the Czech took a one-set lead in 34 minutes.
Pliskova carried the momentum into the second set as she went a break up at the first time of asking, but Muguruza found some form to earn a double break and fire a warning shot at her opponent.
Pliskova responded by snatching serve, which forced the set into a tie-break, and it was the Spaniard who came out on top 7-4.
Muguruza took full control of the third set as she ripped through to take a 4-0 lead, but Pliskova showed her fighting spirit to climb up to 3-5 with two breaks of serve.
The world number five eventually completed her comeback to cement victory.