they will (should) light up around midnight, because the cheap off peak supply is overnight.
they store heat during the night, and let it out during the day.
it will take you a few days to find the settings that suit you. You can adjust input (amount of heat stored) and output (how fast it comes out).
If you are out of the house all day, close the outlet shutters, or they will give out all their heat while you are not there to enjoy it, and be going cool by evening.
They're quite popular with people who are at home all day, and get up and go to bed early.
If your bedroom is cold, get a small oil-filled electric radiator and run it at night (with a thermostat and preferably a timer) because the storage heaters will have run down by evening. The way the meter works, your radiator and other appliances will (probably) get the benefit of the cheap rate, for electricity used during the offpeak hours.
You may need to sit up next to the meter to see what time it switches over. Switching times are deliberately staggered to prevent a big power usage surge if every house came on together.