Hi Mark
It would be a good move, if you could, to remove the top rad hose, together with the bottom one, and get a hose pipe in there just to give it a good flush.
Pouring water into the expansion bottle, as you are doing, will clear the engine block.
So - with that being done, refill the system with water and start up, and see how long it takes to boil over.
When the thermostat opens, the radiator and top hose gets hot - but not before then. I'm not trying to be patronising here, but are you sure you put the stat in the correct way round? Thats important.
So - if the fault persists - and I've got a funny feeling it will, the next step is to have a garage check for combustion gases in the air space above the coolant. This is done by bubbling the gas through a blue liquid - the liquid turns yellow if combustion gas is present.
Its a long job to access the water pump as the timing belt has to come off, so its worthwhile trying to rule out the simpler things first.....I'm just sorry I can't be more specific!
John