The very pin delivering the signal is the charge/discharge channel.
The voltage over the cap will not be constant, but have a ripple, roughly a sawtooth. How much depends on the size of the cap and the total series resistance (which includes the internal resistance of the pin, the capacitor, the wiring, and whatever resistor is in between the pin and the cap). Stray inductance may also play a role. Connect a scope to see this ripple. The cap charges during the high part of the PWM cycle, discharges during the low part of the cycle.
Your multimeter will indicate a constant voltage as it averages out the ripple.
