Positional isomers are a subset of structural isomers. A structural isomer is just a chemical that has the same empirical formula (C6H10N or whatever), so it can really refer to two very different chemicals (there's an endogenous hormone that's a structural isomer of THC, for example). Structural isomers have the same number of each type of atom, but can have those atoms arranged in any structure, and might look nothing like each other. A positional isomer is a special case where the hydrocarbon skeleton is the same, but functional groups are at different positions (like 5-OH-DMT and 4-OH-DMT, for example). So, all positional isomers are also structural isomers, but the former is a much narrower group. We might reasonably expect positional isomers of drugs to also be functional analogues, whereas knowing that two chemicals are structural isomer is pretty useless to us, given that they aren't necessarily structural analogues.