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Yes. Each radiator and the wall thermostat are their own "zone". So if one shows a temp lower than they are set, the boiler will fire. If the other rads show as being up to temp, they will close. I have three non TRV rads; hallway, kitchen and bathroom, so if anything calls for heat, they heat up too. But the hallway one is useful as it keeps the core of the house warm/dry and the other two are tiny rads. It's nice to have a toasty/dry bathroom and the kitchen one is in the laundry area so again handy to deal with any humidity caused by the washing machine/drier.
So you can call for one radiator to come on via the app and the boiler will fire up?