Just a quick update on this.
I had been thinking about the 'pooling air' theory before the heater matrix.
On the drive home this evening I had again issues with overheating. The vents would go cold, the car would start to overheat and raising the revs to 5k would enable heat to come through the vents and the car would cool down to the normal level. This would repeat over and over. On coming into the estate the car would overheat.
My theory was that the restriction in the heater matrix wouldn't allow the air to be pushed through as the cooling system was filled with water. Only with increased revs and pressure from the water pump would enable the air to be pushed through, hence getting heat to the vents.
So this evening I raised the revs in the street (must have looked like a right hooligan) to get heat into the vents before switching the car off. The theory being that the heater matrix would now be full of water and the air past it, enabling it to be bled out. I went to bleed the system and only water came out. So I raised the front end and let it cool down.
I then popped off the top hose - full of air! So I filled with coolant through that hose and connected everything back together in the hope it would solve the problem....
I took it out for a drive, and immediately got constant heat through the vents rising with water temp (above 2k rpm again) and, most importantly, no overheating! I came back into the estate and again no overheating.
So whilst this appears to have solved the overheating issue (tomorrow will let me know better), I think I'll have to replace the heater matrix (which only appear to be available abroad!). The rest of the cooling system has been replaced (with good reason I would assume). That job can wait until I get the dash out to fit the extended leather.
I'll pop an update in tomorrow after a longer run to a course I'm on!