[guided]We need an admissible transport plan between $\mu_s$ and $\mu_t$. The construction should remember that both $\mu_s$ and $\mu_t$ were produced from the same pair $(x,y)$ sampled according to $\pi$. This is why we define a map that records both intermediate positions at once.
For fixed $s,t \in [0,1]$ with $s \le t$, define the map $S_{s,t}: \mathbb{R}^n \times \mathbb{R}^n \to \mathbb{R}^n \times \mathbb{R}^n$ by
\begin{align*}
S_{s,t}(x,y) = (T_s(x,y),T_t(x,y)).
\end{align*}
This map is Borel measurable because $T_s$ and $T_t$ are continuous maps from $\mathbb{R}^n \times \mathbb{R}^n$ to $\mathbb{R}^n$. We define
\begin{align*}
\pi_{s,t} := (S_{s,t})_\#\pi.
\end{align*}
Thus $\pi_{s,t}$ is the law of the pair of random points obtained by starting at $x$, ending at $y$, and observing the straight-line interpolation at times $s$ and $t$.
To prove that $\pi_{s,t}$ is a coupling of $\mu_s$ and $\mu_t$, we check its two marginals. Let $\operatorname{pr}_1,\operatorname{pr}_2: \mathbb{R}^n \times \mathbb{R}^n \to \mathbb{R}^n$ denote the coordinate projections. The first coordinate of $S_{s,t}(x,y)$ is $T_s(x,y)$, so
\begin{align*}
\operatorname{pr}_1 \circ S_{s,t} = T_s.
\end{align*}
Using the identity $(f \circ g)_\#\nu=f_\#(g_\#\nu)$ for pushforward measures, we get
\begin{align*}
(\operatorname{pr}_1)_\#\pi_{s,t} = (\operatorname{pr}_1)_\#(S_{s,t})_\#\pi = (\operatorname{pr}_1 \circ S_{s,t})_\#\pi = (T_s)_\#\pi = \mu_s.
\end{align*}
The same computation for the second coordinate gives
\begin{align*}
(\operatorname{pr}_2)_\#\pi_{s,t} = (\operatorname{pr}_2)_\#(S_{s,t})_\#\pi = (\operatorname{pr}_2 \circ S_{s,t})_\#\pi = (T_t)_\#\pi = \mu_t.
\end{align*}
Hence $\pi_{s,t}$ has first marginal $\mu_s$ and second marginal $\mu_t$, which is precisely the statement that $\pi_{s,t} \in \Pi(\mu_s,\mu_t)$.[/guided]