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Still sounds like it could be a radiator cap. I had similar issues even with a new cap (trident). Eventually fitted a CPC radiator cap and that solved the problem. The CPC cap has a slightly different style of seal.
The engine temp will actually increase slightly when it is first shut down because there is still a lot of heat in the cylinder heads but the coolant is no longer moving to take that heat away. Because of this the pressure in the coolant system will actually increase and if the radiator cap is a bit suspect it will let more coolant out allowing the pressure to drop which will in turn actually lets the coolant boil (worst case).
The engine temp will actually increase slightly when it is first shut down because there is still a lot of heat in the cylinder heads but the coolant is no longer moving to take that heat away. Because of this the pressure in the coolant system will actually increase and if the radiator cap is a bit suspect it will let more coolant out allowing the pressure to drop which will in turn actually lets the coolant boil (worst case).