You say the pump is OFF?
This situtation is specifically known as 'pumping over' so I suggest when this is occuring, the pump is running. No pump, no water movement.
Could be down to a faulty boiler thermostat (however this is unlikely if you are getting a cooler shower), but don't write it out as a possibilty.
More commonly, the pump setting is too high for the system or wrongly positioned due to poor design of system installation, (ie: Open vent and cold feed not 'close coupled').
Is the water in the F&E cistern red/brown in colour?
It would suggest this has been occuring for some time.
For a temporary solution, try turning the pump speed down to see if it cures the problem, the longer term solution would involve altering the system design, could be as simple as close coupling open vent and cold feed or raising the F&E cistern to a higher position.
Carefree, July 2010