[guided]We are checking that the map $\psi_i$ — which inserts a $1$ in the $i$-th coordinate slot — undoes the chart map $\varphi_i$ — which divides through by the $i$-th coordinate. Both operations work with homogeneous tuples, but they live on different sides of the equivalence relation, so we need to be careful.
\textbf{Computing the composition on a representative.} Pick $[x_0 : \cdots : x_n] \in U_i$ — by hypothesis, $x_i \neq 0$. Apply $\varphi_i$: rescale the representative by dividing every coordinate by $x_i$, then drop the $i$-th coordinate (which is $1$), to get
\begin{align*}
\left(\frac{x_0}{x_i}, \ldots, \frac{x_{i-1}}{x_i}, \frac{x_{i+1}}{x_i}, \ldots, \frac{x_n}{x_i}\right) \in \mathbb{A}^n_k.
\end{align*}
Now apply $\psi_i$: re-insert a $1$ in the $i$-th slot, yielding the homogeneous class
\begin{align*}
\left[\frac{x_0}{x_i} : \cdots : \frac{x_{i-1}}{x_i} : 1 : \frac{x_{i+1}}{x_i} : \cdots : \frac{x_n}{x_i}\right].
\end{align*}
\textbf{Are we back where we started?} The representative we have now is the original $(x_0, \ldots, x_n)$ scaled by $1/x_i$ — every entry has been divided by $x_i$, including the $i$-th entry which is $x_i/x_i = 1$. By the equivalence relation defining $\mathbb{P}^n_k$, scaling a representative by a non-zero element of $k$ does not change the equivalence class. Specifically, multiplying our representative back by $\lambda = x_i \in k^\times$ yields
\begin{align*}
\left(\frac{x_0}{x_i} \cdot x_i, \ldots, 1 \cdot x_i, \ldots, \frac{x_n}{x_i} \cdot x_i\right) = (x_0, \ldots, x_n),
\end{align*}
which is the original representative. So the homogeneous class is the same:
\begin{align*}
\psi_i(\varphi_i([x_0 : \cdots : x_n])) = [x_0 : \cdots : x_n].
\end{align*}
\textbf{Where does $x_i \neq 0$ get used?} In two places. First, $\varphi_i$ requires dividing by $x_i$, which only makes sense when $x_i \neq 0$ — that is exactly the condition defining $U_i$. Second, the rescaling by $\lambda = x_i$ when comparing equivalence classes requires $\lambda \in k^\times$, again using $x_i \neq 0$.
\textbf{Why this fails outside $U_i$.} If we tried to define $\varphi_i$ at a point with $x_i = 0$, division would be undefined. The point $[1 : 0 : \cdots : 0] \in \mathbb{P}^n_k$ for instance lies in $U_0$ but not in $U_i$ for $i \neq 0$. The collection of charts $U_0, \ldots, U_n$ is necessary precisely because no single one covers all of $\mathbb{P}^n_k$.[/guided]