Will turning my mains water off stop water leakage when replacing a rad?

No turning water off at stop tap,won't make any difference as its two separate systems, dont touch mains water at all . You will need to drain down your heating system as it is a pressurised system ,i would get a professional plumber in to do this ,as it will need repressuriseing again when the valve as been changed and checked ie balancing i hope this helps

make sure filling loop is closed,drain system, alter pipework if you have to,refill system,fit rad,fill with corrosion proof fluid and test.

As you have a combi boiler, there is no need to turn the mains off. If the rad is on the ground floor , you will need to drain the system. You could release the pressure from the valves into a bucket. If your quick once the pressure has gone and change one valve at a time. Will be even easier if it's on the top floor. Ensure you protect any carpet from dirty water and sludge. Or get a plumber if your not confident.

Only if you have a gravity tank feed system but generally most houses now have combi boilers Or sealed systems. If you won’t to change the rad valves your options are 1. Find a drain off point on the system lower if possible or sane level. Out a hose pipe and open drain piont. After approx 5 min open the air vents on the rads starting from the highest in the Biulding and work your way down giving a couple of minutes between each rad ( if water comes out of air vent , check hose to make sure it’s draining or it could be still a lot of water in the system. Lastly open the valves on the rad you remove and catch the last of the water in the pipe work 2. You could freeze the pipes either side of the rad valves ( follow freeze instructions open the valve first to make sure it’s frozen ) 3. You could snatch the valves . If the area needs decoration and flooring then you could have the new valveS at the ready shut almost off , (Depressurise the heating system then open a couple of air vents into a bucket) then remove and replace the valve semi live but be warned as this can be very very messy if you inexperienced. Before you start make sure you have the exact size rad , as old ones may be imperial size ( if it is , you can buy rad extensions to get rad to fit without altering the pipe work)