Arduino startup behaviour

If anything flashes threw the digital pins on start up it will be so quick it won't effect anything.

Your sentence there is a bit broken. I assume your wanting to use the arduino to power on or reset a PC? To do this you don't want the power and reset to be directly wired to the Arduino. I suggest you have the PC connect to a pair of relays and have the Arduino actuate the relays. One that actuates on 5V. The you can digitalWrite HIGH to a pin that connects to the relay. The Relay will then actuate and turn on the PC. Here is a slightly modified version of the button example.

 // constants won't change. They're used here to 
 // set pin numbers:
 const int buttonPin = 2;     // the number of the pushbutton pin
 const int ledPin =  12;      // the number of the relay pin

 // variables will change:
 int buttonState = 0;         // variable for reading the pushbutton status

 void setup() {
   // initialize the relay pin as an output:
   pinMode(ledPin, OUTPUT);      
   // initialize the pushbutton pin as an input:
   pinMode(buttonPin, INPUT);     
 }

 void loop(){
   // read the state of the pushbutton value:
   buttonState = digitalRead(buttonPin);

   // check if the pushbutton is pressed.
   // if it is, the buttonState is HIGH:
   if (buttonState == HIGH) {     
     // power on to relay:    
     digitalWrite(ledPin, HIGH);  
     delay(500); // allows power to the relay to stay on long enough 
                       // for the PC to power on. this number may need to 
                       // be adjusted
   } 
   else {
     // send no power to the relay
     digitalWrite(ledPin, LOW); 
   }
 }

Of course the button will be replaced with whatever means you plan to use to tell the board to actuate the relay.