Given a triangle ABC, with known sides a=BC and b=AC, and known angle A, we wish to find angle B.
This is a typical application of the Sine Rule (Law of Sines).
In some circumstances, the sine rule gives an ambiguous result: with two possible solutions for angle B.
I am trying to find the simplest way of identifying whether or not the sine rule would give a unique solution.
Is it true to say that the sine rule will give a unique solution to this problem iff a > b?

The question isn't really (or shouldn't be) about the sine rule, but about when two sides and an angle not formed by the two sides determine a unique triangle. You found almost the right criterion; in fact if $a=b$ the triangle is also uniquely determined (unless you allow degenerate triangles). The sine rule, by contrast, always allows two different angles at $B$, since the sine is symmetric with respect to reflection at $\pi/2$. If $a\ge b$, you can exclude the greater of the two because the sum with the angle at $A$ would exceed $\pi$, whereas for $a\lt b$ both of these angles correspond to triangles.