The main difference is that 'ao' is a noun and 'aoi' is an adjective
For example, if you are saying that you like the colour blue, you would say "watashi wa ao ga suki desu".
If you were referring to something that's blue, eg a pencil, you would say "aoi enpitsu".
'Aka wain' is different because 'red wine' can be considered a noun in whole.