XLR+RCA doesn't mean the same voltage through both outputs, but signal through both outputs simultaneously (4.2V xlr and 2.1V rca)
This is the point, he's saying that when he selects Analog RCA the RCA volume is - say - 2.1V, and when selecting XLR/RCA the same RCAs are higher in voltage (not saying it's exactly 4.2, but could be...) And this is very weird to me... shall we ask @mirror for comments?
I know that. You know that. Almost everybody knows that. The question remains, though, according to the OP...
He should check the volume levels first. When he switches between xlr and xlr+rca outputs the volume level on each output can be different. Maybe he decreased the volume level while using the "xlr" output and then switched to the xlr+rca output where the volume level was higher ("startup volume" setting?).
It was volume matched, had them both set to -40 In the end I did a factory reset of the A8 and now using RCA both 'Analog-RCA' and 'XLR/RCA' have the same volume.