Your ideal (though not often something you can hear) is XLR to XLR.
One reason to go TO an XLR at the amp is when the XLR inputs have greater impedance than the RCA equivalents, often XLR inputs are double. If the preamp is sensitive (like many tube preamps are) then the higher the input impedance of the amp, the better.
Using an XLR output to RCA may help isolate from ground loops as the RCA pin and shield will be actively driven, with very high impedance to ground and the shield only connected on one end.
Best,
Erik