I remember reading about the following example a while back in one of Steenrod's papers on cohomology operations. If we look at $S^3\vee S^5$ and $\Sigma \mathbb{C} P^2$, these spaces have isomorphic cohomology rings over $\mathbb{Z}$, because cup products in the cohomology of a suspension are always zero. However, because Steenrod squares are stable, we have a non-trivial $Sq^2$ acting on $H^3(\Sigma \mathbb{C} P^2)$, and thus these spaces cannot be homotopy-equivalent.
Is there another quick, or elementary, way to distinguish these spaces?
We can also distinguish them using homotopy groups. Note that $\mathbb{C}P^2$ is the $4$-skeleton of $\mathbb{C}P^\infty$ which is a $K(\mathbb{Z},2)$, and it follows that $\pi_3(\mathbb{C}P^2)\cong \pi_3(\mathbb{C}P^\infty)=0$. Since $\mathbb{C}P^2$ is simply connected, the suspension map $\pi_3(\mathbb{C}P^2)\to\pi_4(\Sigma\mathbb{C}P^2)$ is surjective by the Freudenthal suspension theorem, so $\pi_4(\Sigma\mathbb{C}P^2)$ is trivial.
On the other hand, $\pi_4(S^3)\cong \mathbb{Z}/2$ and $S^3$ is a retract of $S^3\vee S^5$, so $\pi_4(S^3\vee S^5)$ is nontrivial. Thus $S^3\vee S^5$ cannot be homotopy equivalent to $\Sigma\mathbb{C}P^2$.
(Of course, this raises the question of how we know that $\pi_4(S^3)$ is nontrivial, which probably cannot be shown by any means that are easier than the Steenrod square argument you mentioned, and indeed some commonly used ways to prove it are very closely related to the fact that $Sq^2$ is nontrivial on $H^2(\mathbb{C}P^2)$.)