You are trying to make your system fit a "C Plan" which is quite a rare setup (even though the site you link to says it is a common system).
If you truly do have a C Plan, then you should of had the 6 wire valve installed, and not the 5 wire. You could either swap the head with a new one (no plumbing involved, but expensive), or add a relay to take place of the changeover contacts. Perhaps not particularly straight forward for a DIYer.
HOWEVER, if you have the wrong valve fitted, and are missing the white wire, I cannot see how the pump would fire up unless the time control and stat called for it. So your rads would not get hot just because the HW was on....
There must therefore be another incorrectly wired part, possibly when the valve was swapped. Has the pump and boiler been wired into the same terminal?