I will write $S^n(r)$ for the round $n$-sphere of radius $r$. It is well known that the scalar curvature is a constant $\frac{n(n-1)}{r^2}$.
Now, for two positive real numbers $r,s$, consider the Riemannian product $S^2(r)\times S^2(s)$. This has scalar curvature $\frac{2}{r^2} + \frac{2}{s^2}$.
A relatively uninspired calculation shows that the scalar curvature has the constant value $2$ if and only if $r = \frac{s}{\sqrt{s^2-1}}$. (The value of $2$ was picked just to make this formula nice - nothing that follows depends critically on this choice.) In particular, there are infinitely many distinct pairs $(r,s)$ which give the same scalar curvature.
However, I claim that "most" of these pairs $(r,s)$ give different local isometry types. Specifically, the unordered pair $\{r,s\}$ controls the local isometry type. More precisely, I claim:
Proposition If $S^2(r)\times S^2(s)$ and $S^2(r')\times S^2(s')$ are locally isometric, then $(r,s)$ is a permutation of $(r',s')$.
Proof: We will assume without loss of generality that $r\geq s$ and that $r'\geq s'$.
Now, at every point of $S^2(r)\times S^2(s)$, the maximum sectional curvature of a two-plane is obtained by a $2$-plane tangent to the $S^2(s)$ factor, and it has sectional curvature $\frac{1}{s^2}$. Since local isometries preserve maximum curvature at a point, we must have $1/s^2 = 1/s'^2$, which easily implies $s = s'$. Moreover, the existence of a local isometry implies the scalar curvatures match, so $\frac{2}{r^2} + \frac{2}{s^2} = \frac{2}{r'^2}+\frac{2}{s'^2}$. As we already know $s = s'$, this simplifies to $\frac{2}{r^2} = \frac{2}{r'^2}$, which then implies $r= r'$. $\square$.
One can play a similar game with $S^m(r)\times S^n(s)$ as long as both $m,n\geq 2$. In particular, there are infinitely many such examples in each dimension $4$ or larger. However, one can not play this game with, say, $n=1$, basically because $S^1(s)$ is locally isometric to $S^1(s')$ even if $s\neq s'$. So the above approach won't work in dimension $3$.
However, there are three dimensional examples: the Berger spheres. A Berger sphere is obtained as follows: start with a round $3$-sphere $S^3(r)$ and the shorten the metric in the directions tangent to the Hopf fibration. If these directions are shortened by a factor of $t < 1$, then one can compute the resulting metric is homogeneous, and that, in an appropriate orthonormal basis of $T_p S^3$, that $K(X,Y) = K(X,Z) = r^2t^2$ while $K(Y,Z) = r^2(4-3t^2)$.
It follows that the scalar curvature is constant with value $r^2(8-2t^2)$. In particular, one can find infinitely many pairs $(r,t)$ with the same scalar curvature. However, note that for different choices of $t$, the ratio $\frac{\max{\text{sectional curvature}}}{\min{\text{sectional curvature}}} = \frac{4-3t^2}{t^2}$ is a local isometry invariant. In particular, $t$ is determined by the local isometry tyrpe, so there are infinitely many examples of different local isometry types but the same constant scalar curvature.