Its pretty easy.... I have not had my Toledo long so not done any work on it yet but from looking at it my old VW Polo, which I changed, is the same...
1. Undo the bolts that hold the plastic housing to the block (It will start to leak all of the coolant out but just undo them all and dump the water on the floor)
2. Remove the old O'ring from the housing and clean both surfaces of the housing and block.
3. Place in the new o'ring (Whether you use some sealant too is up to you... Personally I feel if it needs sealant then you are doing it wrong)
4. Replace the housing but do not tighten it too much or you will break the plastic housing... (About £80 at the dealer)
5. Fill back up with some mixed coolant and water (I mix this in a watering can)
6. Start the car and leave it ticking over.
7. Turn the heater system on to hot with the fan full...
8. Leave it running till the tempersture guage is past half and the electric fan has cut in and out twice.
9. Whilst it is running you will see air bubbles coming up in to the expansion tank when it escapes. Keep the tank topped up to the MAX mark with coolant. (All of the coolant may disapear when the Thermostat open and lets all of the coolant in to the radiator.)
10. Check for leaks.....
11. Drink Tea