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The Diccionario Panhispánico de Dudas (see translation to English by Google) claims that the RAE has not considered rr a single letter at least since 1803. There is an entire article explaining the letter r (translation to English) but the most relevant fact is: La letra r, duplicada, forma el dígrafo rr Which means The letter r, duplicated, is ...

While I don't have an authoritative source, these two facts seem to suggest rr was never a single letter: When learning the alphabet, we used to include ch and ll in the sequence, but not rr The "Traditional Spanish" database collation considers ch and ll when sorting, but not rr

I think you're talking about the NATO phonetic alphabet used for radio communications. In this website they say they it is used with the English words though numbers may be translated to local language. Also there are equivalent spelling alphabets in other languages: you can read them here. So for Spanish it would start with Antonio, Barcelona, Carmen, ...

I once had the opportunity to visit a navigation control center and they gave me a card with the phonetic alphabet they used and it was pretty much the same as NATO phonetic alphabet. I guess (and hope) that for those kinds of official and international things there is some kind of standard. For the everyday use, we use names of cities, provinces, ...