[guided]We first isolate the random quantity to which concentration will be applied. The concentration inequality is a statement about a [measurable function](/page/Measurable%20Function) of independent inputs, so we must define that deterministic function and check measurability.
Let $X_{1:n}:(\Omega,\mathcal A)\to(S^n,\mathcal E^{\otimes n})$ be the vector of observations, defined by
\begin{align*}
X_{1:n}(\omega):=(X_1(\omega),\dots,X_n(\omega)).
\end{align*}
For each $f\in\mathcal F$, define $T_f:S^n\to\mathbb R$ by
\begin{align*}
T_f(x_1,\dots,x_n):=P f-\frac{1}{n}\sum_{i=1}^{n}f(x_i).
\end{align*}
The integral $P f=\int_S f(x)\,dP(x)$ is finite because $a\le f\le b$. The map $(x_1,\dots,x_n)\mapsto f(x_i)$ is $\mathcal E^{\otimes n}$-measurable for each coordinate $i$, hence $T_f$ is measurable as a finite linear combination of measurable real-valued functions plus the constant $P f$.
Now define $z:S^n\to\mathbb R$ by
\begin{align*}
z(x_1,\dots,x_n):=\sup_{f\in\mathcal F}T_f(x_1,\dots,x_n).
\end{align*}
The countability of $\mathcal F$ is used exactly here: a countable supremum of measurable real-valued functions is measurable. Without countability, this step would require an outer-probability or separability convention.
The function $z$ is also bounded. Since each $f$ takes values in $[a,b]$, the integral average $P f$ lies in $[a,b]$, and every empirical average $\frac{1}{n}\sum_{i=1}^{n}f(x_i)$ also lies in $[a,b]$. Therefore, for every $f\in\mathcal F$ and every sample point $(x_1,\dots,x_n)\in S^n$,
\begin{align*}
-(b-a)\le P f-\frac{1}{n}\sum_{i=1}^{n}f(x_i)\le b-a.
\end{align*}
Taking the supremum over $f\in\mathcal F$ preserves finiteness, so $z$ is a bounded measurable map. Consequently
\begin{align*}
Z:=z(X_{1:n})=\sup_{f\in\mathcal F}(P f-P_n f)
\end{align*}
is a bounded real-valued random variable.[/guided]