In general, protective devices operate faster, the greater the current.
As such as the current exists for a shorter period of time, there is less heating of conductors.
This results in a smaller CSA being required.
MCBs are an oddity, because they utilise two methods to operate.
An electromagnetic coil and a Bi-metallic strip.
In the tables in Appendix 3, these are represented by the straight line for the electromagnetic coil and the curve for the Bi-metallic strip.
The tables only show the amperage required for the MCB to operate within the times specified by BS7671, 0.1s to 5s.
Without having the manufacturer's time/current curve available, it is quite likely that this Amperage will also cause the MCB to operate instantaneously (within 0.01s).
When you start picking and mixing the values, choosing one that is measured, and another that is tabulated, you will when conducting the adiabatic equation obtain a result that produces a higher value for CSA than is actually required.
If you wish to use the measured value of PEFC 800A, you should not use the tabulated time values in the tables in Appendix 3, but those of the manufacturer.
If you wish to use the tabulated time values from the tables in Appendix 3, then you should also use the tabulated current values.