You can target a specific occurrence with the rewrite tactic using the suffix at N. Occurrences are numbered from 1 in left-to-right order. You can rewrite multiple occurrencess by separating their indices with spaces. You need Require Import Setoid. The at suffix is also available with some other tactics that target occurrences of a term, including many tactics that perform conversions (change, unfold, fold, etc.), set, destruct, etc.
intros.
rewrite -> (comm a b) at 2.
rewrite -> (comm _ _).
reflexivity.
There are other possible approaches, especially if all you need is to apply equalities. The congruence tactic can find what to rewrite and apply symmetry and transitivity on its own, but you need to prime it by adding all equivalences to the context (in the form of universally-quantified equalities), it won't query hint databases.
assert (Comm := comm).
congruence.
To get more automation, Hint Rewrite creates a database of theorems which the tactic autorewrite will try applying. For more advanced automation, look up generalized rewriting with setoids, which I'm not sufficiently familiar with to expound on.