First, I need to point out a common pitfall. The coordinate rings $k[W]$ and $k[V]$ actually have the structure of $k$-algebras. We definitely have a bijection between regular maps $f : V \to W$ and $k$-algebra homs from $k[W] \to k[V]$. But that does not mean we have a bijection between regular maps and ring homs. In fact, we don't. For a concrete example of a ring hom that isn't a $k$-algebra hom, see here. Ok, on with the show!
As is mentioned in the comments, we need a bit more of an argument to check injectivity. However your broad idea can still be salvaged:
First, let $f \neq g \in \text{Hom}(V,W)$. Since $f \neq g$, we can find an $x_0$ with $fx_0 \neq gx_0$. Then the maximal ideals corresponding to $fx_0$ and $gx_0$ in $K[W]$ are distinct, so we can find a function $\varphi \in K[W]$ which is in one ideal (say, $\mathfrak{m}_{fx_0}$) but not the other ($\mathfrak{m}_{gx_0}$). But now we see $\varphi f x_0 = 0$ and
$\varphi g x_0$ is not $0$. So $f^* \varphi \neq g^* \varphi$, and $f^* \neq g^*$.
As for surjectivity, it's a bit harder to figure out without having seen the argument before. The idea is to use the coordinate functions on $W$ to tell us where a point in $V$ must be sent.
Let $\varphi : k[W] \to k[V]$, and write $k[W] = k[w_1, \ldots, w_n] / I(W)$. Recall in this context $w_i$ is the function sending a point in $W$ to its $i$th coordinate.
Now we define $v_i = \varphi w_i \in k[V]$. These assemble to give us a map
$f : V \to \mathbb{A}^n$ defined by $f(p) = (v_1 p, v_2 p, \ldots, v_n p)$. You should meditate some on the construction of this map, and why it should be an obvious thing to consider. We're taking a point in $V$, and seeing where it must go if we want our map to be compatible with $\varphi$.
It's now routine to check that $f$ actually sends $V$ to $W$. Moreover, we can check (and you should) that $f^* = \varphi$. Though again, we cooked up $f$ to make this work.
I hope this helps ^_^