If I choose a CDP with say, 4V output at XLR, will it mean that my amp will ultimately see 8V at the MAX level of the preamp's output?Assuming you are referring to an active (not passive) preamp, when its volume control is at max its output voltage will usually be several times or more greater than its input voltage, regardless of whether balanced or unbalanced connections are used. In other words, an active preamp applies significant gain to the signal internally, for both types of connections, when its volume control is at max.
Regards,
-- Al