The accusative is the default in English. If I pointed to you in the picture and said "who is that", you would say "me", not "I". Generally in a non sentence like the photo label, "me" or "us" would be appropriate.
Curiously, if you make it a sentence, "This is John, Valencia and I on vacation" you would use "I" here, but only because you would be using a special verb form, called a copula, meaning the nominative "I" is used as the verb's compliment.
If the caption said "Valencia kissing me on vacation" (or "Valencia punching me on vacation" depending on your relationship with Valencia) you would use the accusative "me".