Why you should know: The ‘a’ vs ‘an’ conundrum is not about what letter actually begins the word, but instead about how the sound of the word starts.
For example, the ‘h’ in ‘hour’ is silent, so you would say ‘an hour’ and not ‘a hour’. A trickier example is Ukraine: because the ‘U’ is pronounced as ‘You’, and in this case the ‘y’ is a consonant, you would say “a Ukraine” and not “an Ukraine”.
Tip: when in doubt, sound it out(loud).
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NASA vs NSA makes this more apparent too. For example:
A NASA investigationvs
An NSA investigation