They both use the same virus database, so technically it would be the same, however, it also depends on the settings that you use in either scan.
The boot-time scan is normally used if a detection is found in the normal windows mode and avast can't deal with the problem whilst windows is running, e.g. a file in use by another program, virus in memory, etc.
It is at those times that you would schedule a boot-time scan, it isn't there as a substitute to the conventional on-demand scans this you run periodically (you decide the duration, etc.).