For hot water set the combi or cylinder to 60 centigrade, this is not only for achieving optimum hot water quantity it is also to kill off any bugs that occur naturally in water systems.
Run the boiler on maximum, this will give you maximum output on the radiators and thereby heat the house quickest, it will also mean the cooldown period of the radiator will be longer thereby retaining more heat for longer which will be transmitted after the boiler has gone OFF
Run you system 24/7 so that the property remains heated and doesn't need to heat up from cold as it would if you set time periods, when the house is unoccupied as you are out at work the heat will be maintained as it is also the use of doors and windows that lose heat to a property.