Thank you very much. I read that to mean the modulating down won't occur with a simple on/off control, because it will switch off and prevent that occurring.
Yes
With Nest if I set the controls to switch off at 8pm does it mean it'll automatically throttle the boiler down as that time approaches, rather than a sudden cut off?
Not really, it's more temperature related than time related. If you set the room temperature on the thermostat to 20C as the room approaches that, the boiler output temperature will slowly decrease so that at the end when it hits 20C the radiators may only be lukewarm anyway. Which will depend upon the heat the property requires to keep the set temperature. i.e. if the radiators are big enough to allow the water temperature to drop and still maintain the room temperature, and also the outside temperature.
I don't have Nest myself, so can't be sure on what would happen at 8pm in your scenario. However, it is called a learning thermostat and some users do report it doing strange things for a while whilst it's learning how you use the heating in your home, so it might well do. I can't imagine it would do it unless the set temperature was reached as it will assume that you want to maintain the temperature you've selected until 8pm, and if it throttles down much before, the room could cool down before it's 8pm. However, in theory, if the system has been sized correctly, it will likely have already modulated to a lower setting as it should be at the set temperature by the end of the day anyway. Maybe a bone fide user will be along and be able to tell you for certain how it works in practice.
would the boiler itself not modulate down as the target water temperature is approaching, regardless of smart controls?
Their burners do modulate to control the water temperature, but AFAIK usually the water temperature doesn't change. You would have to check the specification of the one you are interested in to be sure.
Condensing boilers work more efficiently with cooler return water temperatures, so some can modulate the burner to prevent the return water getting above a certain temperature, others modulate to maintain a fixed flow temperature.