Hmm.. both affect the signal, so I can measure and adjust for any distortions. But I think I would take calibrating a VCR to mean adjusting something on the VCR, which might mean taking it apart and turning some pots on the circuit board, which is probably a normal procedure in the factory or repair.
I think I learned something quite interesting today. I noticed the peak on my test of VCR frequency response. Next, I looked at the datasheet for a head amplifier. Three things I've learned;
1 I thought I could connect a digitzer straight to the heads and somehow get a better quality signal. In fact, the single chip head amplifier directly outputs the VCR signal, which means it demodulates the FM signal. So nothing as simple as touching a digital oscilloscope to a couple pins. Also, changing out this one chip for a better one might give less noise or different sharpness.
2 Some issues with layout can cause the peaking I've observed. So I know my VCR might not be good quality. I also know it can be fixed by soldering a single part. Or I can do this in software.
3 The head amplifier directly combines Y and C signals, so in fact having s-video in is pointless

I want to check this with a few more chips. I've always wondered this; first I read that the "color-under" method means the signals are separate, but instead they are just separated by the amplifer. So I want to do more research.