Jimjoyce, The XLR connector is just a better design than an RCA one. Thinner pins for less eddy current problems, better contact, firmer connection, etc. This is not to say that ALL XLRs will sound better than ALL RCAs, because as you infer there has been quite a lot of development in RCA connectors, largely to overcome their inherent problems. BNC connectors are inherently way better for single-ended audio and should have been the standard, at least for high-end stuff. The RCA connector is only about convenience.
Nrenter makes a great point. I recently found this out when I was ordering a DIN to XLR phono cable from a guy on eBay who makes them cheaper than what I have to pay for the individual parts. He had no idea how to construct a balanced cable, even though he is in the business. He built it to my specs finally, with separate but equal conductors for the positive and negative halves of the signal and the shield separately grounded. I have not done the research to determine whether this problem is common to even megabuck cables. (I paid $70 for the finished cables, which I then terminated myself with my choice of XLRs.)
Nrenter makes a great point. I recently found this out when I was ordering a DIN to XLR phono cable from a guy on eBay who makes them cheaper than what I have to pay for the individual parts. He had no idea how to construct a balanced cable, even though he is in the business. He built it to my specs finally, with separate but equal conductors for the positive and negative halves of the signal and the shield separately grounded. I have not done the research to determine whether this problem is common to even megabuck cables. (I paid $70 for the finished cables, which I then terminated myself with my choice of XLRs.)