The smaller tank is the header tank for the central heating radiators - if the inlet valve is good then water may be entering this small tank through the outlet pipe you mention.
In your hot water storage tank is a heating coil that circulates water from the boiler to warm up either the radiators or the tap water in the tank - a motorised valve decides which way the water goes. Radiators and the coil are topped up by the little tank.
If the coil in the hot water tank has a split or small hole, the water in the big tank has a direct connection with the little tank. Even though the bases of your two loft tanks are level with one another each has a different height of water - with a small hole or split in the heating coil, gravity will be trying to equalise the the water levels of the two loft tanks.
Wait for the overflow to happen - make sure nobody is drawing off hot water - nip up to the loft - test the temperature of the water in the little tank (it should be quite cold) - observe the inlet of the big tank and see if any water is flowing out by the action of the inlet valve.
Alternatively - turn off the boiler and tie up the inlet of the big tank so that no water can enter it and mark the water level - wait. If the overflow stops and the level of the water in the big tank has dropped then there's a hole in the heating coil in the hot water storage tank in you airing cupboard.
You may need a new hot water tank.
Good luck...
Peccavi
September 2009