We cheat a bit, giving a solution that wouldn't work for the space of functions from $X$ to $\Bbb R$:
Of course one possibility is $L(f)=0$ for every $f$. If we assume there exists $f$ with $L(f)\ne0$ then $L(f)=L(1f)=L(1)L(f)$ shows that $L(1)=1$ on the set where $L(f)\ne0$.
If we simplify things by assuming that $L(1)=1$ then there exists $\psi:\Bbb R\to\Bbb R$ with $\phi(f)=f\circ \psi$.
First,
Lemma If $\phi:V\to\Bbb R$ is a homomorphism with $\phi(1)=1$ then there exists $x\in\Bbb R$ such that $\phi(x)=x$ for every $f$.
Proof: Define $i\in V$ by $i(t)=t$. Let $x=\phi(i)$. Then $\phi(i)=i(x)$.
Suppose that $f(x)=0$. Then there exists $g$ with $f=(i-x)g$. So
$$\phi(f)=(\phi(i)-x\phi(1))\phi(g)=0\phi(g)=0.$$
Now for a general $f\in V$, let $g=f-f(x)$. Then $g(x)=0$, so the previous paragraph shows that $\phi(g)=0$. So $$0=\phi(f)-f(x)\phi(1)=\phi(f)-f(x).$$QED.
If $L$ is as in the question and in addition $L(1)=1$ then there exists $\psi:\Bbb R\to\Bbb R$ with $L(f)=f\circ \psi$.
Proof: For each $x\in\Bbb R$ define $\phi_x:V\to\Bbb R$ by $$\phi_x(f)=L(f)(x).$$The lemma shows that for every $x$ there exists $y$ such that $$\phi_x(f)=f(y)$$for all $f$. For a given $x$ there is at most one such $y$, since if $y_1\ne y_2$ there exists $f$ with $f(y_1)\ne f(y_2)$. So we can define $\psi:\Bbb R\to\Bbb R$ by $\psi(x)=y$, and we're done.
If you don't want to assume that $L(1)=1$: Since $L(1)=L(1^2)=L(1)^2$ it follows that $L(1)$ takes only the values $0$ and $1$. Let $A$ be the set where $L(1)=1$ and let $B$ be the set where $L(1)=0$. You can modify the above to show there exists $\psi:A\to\Bbb R$ such that $L(f)(x)=f(\psi(x))$ for $x\in A$ and $L(f)(x)=0$ for $x\in B$.