Yes, NTC thermistors are available in a wide range of values and tolerances. As you say, the temperature/resistance curve is not exactly linear. I did read that it is possible to make it linear, but can't remember how. May be the boiler mfr does this within the PCB.
As far as I am concerned, weather compensation is a method of varying the flow temperature in inverse proportion to the outside temperature; i. e the colder it gets, the higher the temperature. The reason for doing this is that the heat required to maintain a certain temperature in the house is directly proportional to the difference between inside and outside temperatures, so radiator output needs to vary. As the output of radiator varies with water temperature, it is logical to use this fact to obtain the required output.
Incidentally, TRVs work much better if weather comp is used.