I don't know how explicit we can go, but I'll give it a try. We have to go first through the homotopy-theoretical part.
Since $\{ * \} \subseteq X, \{ * \} \subseteq Y$ are cofibrations, $X \vee Y \subseteq X \times Y$ also is. Let $Z$ be a pointed space and consider the long exact sequence of homotopy for the pair $X \vee Y \subseteq X \times Y$, ie. the sequence
$\ldots \rightarrow [\Sigma ^{2}(X \vee Y), Z] \rightarrow [\Sigma(X \wedge Y), Z] \rightarrow [\Sigma(X \times Y), Z] \rightarrow [\Sigma(X \vee Y), Z] \rightarrow [X \wedge Y, Z] \rightarrow \ldots$,
where $[-,-]$ is the pointed set of homotopy classes of basepoint-preserving maps. Note that for any $n \geq 0$, $\Sigma^{n}(X \vee Y)$ is homeomorphic to $\Sigma^{n}X \vee \Sigma ^{n} Y$. I will not distinguish between the two.
Let $k \geq 1$ and define a map
$\psi ^{k}: \Sigma^{k}(X \times Y) \rightarrow \Sigma^{k}X \vee \Sigma^{k}Y$
$\psi ^{k} = \Sigma^{k}(i_{X} \pi_{X}) + \Sigma^{k}(i_{Y} \pi_{Y})$,
where $\pi: X \times Y \rightarrow X, Y$ are the projections and $i: X, Y \rightarrow X \vee Y$ are the inclusions. Addition is performed via the suspension structure on $\Sigma^{k}(X \times Y)$, so this is why we require $k \geq 1$. (Observe that even though I denote it by addition this is not necessarily commutative for $k=1$.)
If $j: X \vee Y \hookrightarrow X \times Y$ is the inclusion, then I claim that $\psi ^{k}$ is the left inverse to $\Sigma^{k}j$, ie. $\psi ^{k} \circ \Sigma^{k}j = id_{\Sigma^{k}(X \vee Y)}$. This is important because $\Sigma^{k}j$ are connecting maps in the long exact sequence of homotopy. Indeed, one computes
$\psi ^{k} \circ (\Sigma^{k}j) = (\Sigma^{k}(i_{X} \pi_{X}) + \Sigma^{k}(i_{Y} \pi_{Y})) \circ \Sigma^{k}j = \Sigma^{k}(i_{X} \pi_{X} j) + \Sigma^{k}(i_{Y} \pi _{Y} j) = \Sigma^{k}(id_{X} \vee const) + \Sigma^{k}(const \vee id_{Y}) \simeq (\Sigma^{k}id_{X} + const) \vee (const + \Sigma^{k}id_{Y}) \simeq \Sigma^{k}id_{X} \vee \Sigma^{k}id_{Y} \simeq id_{\Sigma^{k}X \vee \Sigma^{k}Y}$.
(One can also see this geometrically.) This immediately implies that for all $k \geq 1$ and all $Z$ the $[\Sigma^{k}(X \times Y), Z] \rightarrow [\Sigma^{k}(X \vee Y), Z]$ induced by $j$ is surjective and - by exactness of the long exact sequence - that for all $n \geq 1$ the map $[\Sigma^{n}(X \smash Y), Z] \rightarrow [\Sigma^{n}(X \times Y), Z]$ has zero kernel. In particular, for $k=1$ we have the short exact sequence of groups
$0 \rightarrow [\Sigma(X \wedge Y), Z] \rightarrow [\Sigma(X \times Y), Z] \rightarrow [\Sigma(X) \vee \Sigma(Y), Z] \rightarrow 0$
Moreover, the map induced by $\psi^{1}$ splits it and shows that there is a natural isomorphism
$\phi: [\Sigma(X \wedge Y), Z] \rtimes [\Sigma(X) \vee \Sigma(Y), Z] \rightarrow [\Sigma(X \times Y), Z]$,
of groups, where the product is only semi-direct, because our groups are not necessarily abelian. This is enough for our purposes, since we also have natural bijections
$[\Sigma(X \wedge Y), Z] \rtimes [\Sigma(X) \vee \Sigma(Y), Z] \simeq [\Sigma(X \wedge Y), Z] \times [\Sigma(X) \vee \Sigma(Y), Z] \simeq [\Sigma(X \wedge Y) \vee \Sigma(X) \vee \Sigma(Y), Z]$.
(The second one follows from from the fact that $\vee$ is the direct sum in the category of pointed spaces.) Yoneda lemma establishes that there is an isomorphism
$\theta: \Sigma(X \times Y) \rightarrow _{\simeq} \Sigma(X \smash Y) \vee \Sigma(X) \vee \Sigma(Y) $
in the homotopy category of pointed spaces, ie. a homotopy equivalence that we were after. It takes a little bookkeeping in the above Yoneda-lemma argumentation to see that such map is given by
$\theta = \Sigma(p) + \psi^{i} = \Sigma(p) + \Sigma^{1}(i_{X} \pi_{X}) + \Sigma^{1}(i_{Y} \pi_{Y})$,
where $p: X \times Y \rightarrow X \wedge Y$ is the natural projection. (This is what we get if we start with $id \in [\Sigma(X \wedge Y) \vee \Sigma(X) \vee \Sigma(Y), \Sigma(X \wedge Y) \vee \Sigma(X) \vee \Sigma(Y)]$ and trace it back by all the bijections above to $[\Sigma(X \times Y), \Sigma(X \wedge Y) \vee \Sigma(X) \vee \Sigma(Y)]$ - and this is the way to discover the isomorphisms "hidden" by Yoneda lemma.)
I understand that my exposition is far from perfect, but if you would like me to go into more detail over some parts, please comment.
