The "Bypass Vol" switch is actually a "Bypass | Volume Control" switch. It probably won't make a difference in practice, but to make sure you're getting the
maximum output you should flick the switch to the
left, putting the 3E AUDIO A7 in bypass mode. The potentiometer is bypassed then, ensuring that the volume control knob has no effect and the signal path is as short as possible.
The RCA Gain switch only makes a difference when using thes single-ended RCA inputs, not the balanced XLR inputs. But I guess, you figured that.
Unfortunately, getting the volume "nearer to the AVR" won't buy you much when comparing the sound quality. It is commonly accepted wisdom that for a fair comparison you
must match the level between two devices to much less than 1 dB. Some say less than 0.3 dB. If you don't, then your brain
will play tricks on you, always preferring the louder presentation. This happens on a subconscious level, so even if you know about the effect it's almost impossible to ignore it. Not sure how your entire setup will look like for the comparison, but you really need to find a way to match the levels as closely as possible.
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@TurtlePaul I have no doubts that the A7 technically betters almost all AVRs ever made.