unfortunately going on courses will still not teach you much about a situation like this its a process of educated guess work to work out what goes where orange is the wire that fires boiler or boiler and pump so that leaves just 2 cables to sort out i used to sit down and write what was going where and mark each cable with tape to differentiate between them but now a picture or two on your phone does it take a look in the roomstat will often allow you to match it to one of the remaining cables by putting a meter across the wires you think and switching the stat on and of to confirm this is where the buzzer on the meter comes in handy
actually thats quite a good junction box as often there in a single box and covered in three rolls of insulation tape