As you said before power on capacitor is discharged. Right after power on capacitor is still discharged, so voltage on capacitor is zero, so reset pin has Vcc. With time capacitor gets charges and voltage across capacitor increases and reset voltage becomes closer and closer to ground, until it is ground. But it is important to consider what happens at power down too. At power down capacitor is charged. If power source becomes high impedance at power down, then reset pin will probably go down to zero in time but may take a bit time depending on what source exactly does. But if power source is connected to zero at power down reset pin will observe minus vcc and slowly go up to 0. If reset pin is sensitive it may be a good idea to protect it with a diode.