I'm attempting to prove that if $W$ is a subspace of $V$ and $x \notin W$ that $\exists f \in W^0$ such that $f(x) \neq 0$ where for every subset $S$ of $V$, $S^{0} = \{f \in V^{*} : f(x) = 0 \forall x \in S \}$
My proof is as follows: Suppose $W$ is a subspace of $V$ and that $x \notin W$. $x \in V$, so $x \in V-W$.
Define a functional $f \in V^*$ by $$f(x) = \begin{cases} 0 & x \in W \\ 1 & x \in V - W \end{cases}$$
Then $f \in W^{0}$ because for every subset $S$ of $W$, $x \in S \implies x \in W$, so $f(x) = 0$ and $f(x) \neq 0 \forall x \in V-W$
The answer I have available to me uses a more convoluted argument involving the extension of a basis for $W$. I'm wondering if this is necessary and if my proof is fine as is.
As is pointed in the comments, an extension of a basis for $W$ will be necessary for this, but you can also combine your idea! Suppose that $V$ is finite-dimensional, consider a basis $\beta$ for $W$ and a basis $\alpha$ for $V$ that contains $\beta$. Now define $h : \alpha \to \mathbf F$ by $h(v) = 0$ if $v \in \beta$ and $h(v) = 1$ if $v \in \alpha \setminus \beta$. Then, there is a unique linear extension $f : V \to \mathbf F$ of $h$. It follows that $f$ is your desired linear functional.