I had another look at the actual article/RFC: This is more than just the little endian/big endian byte order, it's about the bit order of serial messages, where, unlike bytes, the bit order could actually be different (for bytes stored in memory the bits of each individual byte in modern / semi-modern computers are always stored in the same order whether it's a LE or a BE memory architecture). In a serial protocol you could send the most significant bit of the stream first, or the least significant bit first, and that's what's at first discussed in that RFC.
Yes, that's right. Since CPUs abstract away the bit ordering, it only starts to matter when dealing with bit-oriented communications. And since it is abstracted away, there's no real benefit to be gained by BE or LE at the bit-level.