I know, likely a silly question. I recognize that Athenian citizenship was only held by citizens, but would only citizens be referred to as Athenians? Or would a metic or slave also be referred to/refer to themselves as an Athenian?
The Greeks referred to individual states by way of their people; as Thucydides famously put it, "the people are the city." While the city of, say, Corinth, existed as a place, political decisions or military actions were taken by "the Corinthians", not by "Corinth".
Who exactly is meant by such a blanket term depended on circumstance. If "the Athenians" decided something in the assembly, the term implied only the adult male citizens who voted on a particular decree. However, when "the Athenians" fled to Salamis and Troizen during the Persian invasions, the term of course meant all men, women, children and slaves who inhabited the city. The word hoi Athenaioi could mean whatever the context required it to mean.
Metics (resident foreigners) would usually not refer to themselves as Athenian, because they were not. A mysterious feature of Hellenistic Athenian grave monuments is that a statistically improbable number of burial inscriptions refer to the deceased as Milesian (i.e. from Miletos in Asia Minor); it's been suggested that the word came to be used as a synonym for metic. Whatever the reason for their self-identification as Milesian, the important point is that they did not call themselves Athenian. On the other hand, metics served in the Athenian army, and as such they could often be subsumed under the term hoi Athenaioi in historical accounts.