[guided]We want a bijection between the two sets. The intuition: a colouring $c$ of $G - e$ with $c(x) = c(y)$ gives $x$ and $y$ a single common colour, and this common colour is precisely what a colouring of the quotient graph $G/e$ assigns to the merged vertex $a$.
Concretely, define
\begin{align*}
\Phi: \mathcal{C}_{=}(G - e) &\to \mathcal{C}(G/e) \\
c &\mapsto \Phi(c), \quad \Phi(c)(v) := \begin{cases} c(v) & \text{if } v \in V(G) \setminus \{x, y\}, \\ c(x) & \text{if } v = a. \end{cases}
\end{align*}
The second branch looks asymmetric — why $c(x)$ and not $c(y)$? Because they are equal: the hypothesis $c \in \mathcal{C}_{=}(G - e)$ gives $c(x) = c(y)$, so we could equivalently write $c(y)$. The map $\Phi$ simply reads the common colour off the pair $(x, y)$ and transports it to $a$.
We must verify $\Phi(c)$ is a proper colouring of $G/e$. Recall that
\begin{align*}
E(G/e) = \{uv \in E(G) \mid u, v \notin \{x, y\}\} \cup \{au \mid u \in V(G) \setminus \{x, y\}, \, ux \in E(G) \text{ or } uy \in E(G)\}
\end{align*}
(edges of $G$ not touching $\{x, y\}$ are kept; edges from $\{x, y\}$ to a vertex $u \notin \{x, y\}$ collapse to a single edge $au$; and the edge $e = xy$ itself disappears, since it would become a loop at $a$).
Take an edge $uv \in E(G/e)$. Two cases.
*Case 1: $u, v \notin \{x, y\}$.* Then $uv \in E(G)$ and $uv \neq e$ (since $e = xy$). So $uv \in E(G) \setminus \{e\}$, and properness of $c$ on $G - e$ gives $c(u) \neq c(v)$. Since $\Phi(c)(u) = c(u)$ and $\Phi(c)(v) = c(v)$, we conclude $\Phi(c)(u) \neq \Phi(c)(v)$.
*Case 2: one endpoint is $a$.* Without loss of generality $v = a$ and $u \notin \{x, y\}$. Then by definition of $E(G/e)$, we have $ux \in E(G)$ or $uy \in E(G)$. In either sub-case the edge lies in $E(G) \setminus \{e\}$ (since neither $ux$ nor $uy$ equals $e = xy$, as $u \neq y$ and $u \neq x$). Properness of $c$ on $G - e$ gives $c(u) \neq c(x)$ (if $ux \in E(G)$) or $c(u) \neq c(y)$ (if $uy \in E(G)$). Either way, since $c(x) = c(y)$, we get $c(u) \neq c(x)$, i.e., $\Phi(c)(u) \neq c(x) = \Phi(c)(a)$.
So $\Phi(c) \in \mathcal{C}(G/e)$.
We now define the inverse $\Psi$: given a proper colouring $c'$ of $G/e$, lift it to $G - e$ by sending the common colour $c'(a)$ to both $x$ and $y$:
\begin{align*}
\Psi: \mathcal{C}(G/e) &\to \mathcal{C}_{=}(G - e) \\
c' &\mapsto \Psi(c'), \quad \Psi(c')(v) := \begin{cases} c'(v) & \text{if } v \in V(G) \setminus \{x, y\}, \\ c'(a) & \text{if } v \in \{x, y\}. \end{cases}
\end{align*}
The verification that $\Psi(c') \in \mathcal{C}_{=}(G - e)$ is the mirror image of the above. First, $\Psi(c')(x) = c'(a) = \Psi(c')(y)$, so the colouring lies in the $=$ class. Second, for an edge $uv \in E(G) \setminus \{e\}$ we check properness: if $u, v \notin \{x, y\}$ the edge corresponds to the same edge in $G/e$ and properness comes from $c'$; if exactly one endpoint, say $u$, lies in $\{x, y\}$, the edge corresponds to $av \in E(G/e)$ and $\Psi(c')(u) = c'(a) \neq c'(v) = \Psi(c')(v)$ by properness of $c'$. There is no case where both endpoints lie in $\{x, y\}$, because the only such edge in $G$ is $e$ itself, which we excluded.
Finally, checking the compositions: $(\Psi \circ \Phi)(c) = c$ because both assignments leave $c$ unchanged on $V(G) \setminus \{x, y\}$ and, on $\{x, y\}$, $\Psi(\Phi(c))(x) = \Phi(c)(a) = c(x)$ and similarly for $y$ (using $c(x) = c(y)$). The reverse composition $(\Phi \circ \Psi)(c') = c'$ is similar. Hence $\Phi$ is a bijection, and
\begin{align*}
|\mathcal{C}_{=}(G - e)| = |\mathcal{C}(G/e)| = P_{G/e}(t).
\end{align*}[/guided]