With a typical two port vale you will have 5 cores. Blue neutral, green/yellow earth, brown switch live from controls, grey permanent live and orange switch live to the boiler. For a standard S-plan you will have 2x two port valves one for heating and the other valve for hot water. If you learn the colours and remember the order of switching then you cant go far wrong especially if you have a drawing in front of you. There is a sticky thread on here in the central heating section with all the standard arrangements. Would be worth printing the schematics off and keeping in a folder in the van. The order of switching goes programmer switches the feed on to the room thermostat or cylinder thermostat depending what channel is timed to go on or switched on at the programmer, thermostat if calling for heat switches the brown on the valve, valve motors round and closes the micro switch between the grey permanent live and orange switch live to boiler. Depending on the type of boiler it may have pump over run so the pump maybe directly connected to the pump live terminal in the boiler. If the boiler doesn't require/have pump over run then it will be connected together with the oranges off the valves and switch live to the boiler.
A y-plan gets a little more harder to explain but again you generally have 5 cores on the valve. Blue neutral, green/yellow earth, white switch live from room thermostat and grey hot water satisfied. The 3port valve can sit in 1 of 3 positions depending on what's being asked of it...port A closed means flow from boiler Is directed to port B which is connected to the coil in the hot water cylinder, port B closed then the flow from the boiler is directed to port A which is connected to the Flow of the radiator circuit, finally the valve can sit in the mid position letting the flow from the boiler down both port A and port B at the same time. With a Y plan you will use the hot water off terminal in the programmer and NC contact on the cylinder thermostat which you wouldn't use on a standard s-plan with spring return valves.