Thanks elied.
Your knowledge of how Canon flash works is surely better than mine. I was aware that Canon's eTTL can measure color temperature and adjust it, but I thought it is to take into account, say, colored-wall reflections, and bring it back to the "standard" flash WB of 5500K. Hence my expectation that when I set camera's WB to "Flash", I shall see it in LR both as "Flash" and 5500K. However, most of my files open at around 6300K, +-200-300K.
There was one extra factor in play I did not mention: I was using Garry Fong's Lightsphere diffuser (the opaque white one) with the white dome attached and positioned directly (i.e., not bounced). I guess that might have "fooled" the flash to consider it non-Canon, or otherwise throw the WB off?
Another question, not related to LR though: when I use the diffuser on my Canon 580EX and 580EX II, it seems that I need to adjust flash exposure on camera between +1.5 and +2 f/stops, to account for the loss of light due to the diffuser. What puzzles me though it that those flashes are supposed to be TTL (i.e., measure light falling on sensor through-the-lens)... if so, shouldn't the camera/flash combination determine the proper exposure even if bounced and diffused, without me having to adjust it so drastically manually?