[guided]We need two facts about the ideal $(X_1 - a_1, \ldots, X_n - a_n)$: it is maximal, and we can compute its quotient explicitly as $k$.
\textbf{The evaluation map.} Send a polynomial to its value at $a$:
\begin{align*}
\mathrm{ev}_a : k[X_1, \ldots, X_n] \to k, \qquad f \mapsto f(a_1, \ldots, a_n).
\end{align*}
This is a ring homomorphism: addition and multiplication of polynomials commute with evaluation. It is surjective onto $k$ because every constant polynomial $c \in k$ has $\mathrm{ev}_a(c) = c$. By the First Isomorphism Theorem,
\begin{align*}
k[X_1, \ldots, X_n]/\ker(\mathrm{ev}_a) \cong k.
\end{align*}
The right-hand side is a field, so the left-hand side is too, which means $\ker(\mathrm{ev}_a)$ is a maximal ideal.
\textbf{Computing the kernel.} The ideal generated by $X_1 - a_1, \ldots, X_n - a_n$ is contained in the kernel: each generator vanishes at $a$, so any $k[X_1, \ldots, X_n]$-linear combination does as well. The opposite inclusion is the substantive content. Why must any $f$ vanishing at $a$ be expressible as $\sum_i p_i \cdot (X_i - a_i)$?
The standard tool is a change of variables. Set $Y_i := X_i - a_i$, equivalently $X_i = Y_i + a_i$. The substitution defines a $k$-algebra automorphism
\begin{align*}
\Phi : k[X_1, \ldots, X_n] &\to k[Y_1, \ldots, Y_n] \\
f(X_1, \ldots, X_n) &\mapsto f(Y_1 + a_1, \ldots, Y_n + a_n)
\end{align*}
(the inverse is the substitution $Y_i = X_i - a_i$). Under $\Phi$, the ideal $(X_1 - a_1, \ldots, X_n - a_n)$ maps to $(Y_1, \ldots, Y_n)$, and the evaluation $\mathrm{ev}_a$ becomes the evaluation at $0$:
\begin{align*}
\mathrm{ev}_a(f) = f(a) = (\Phi f)(0) = \mathrm{ev}_0(\Phi f).
\end{align*}
After this change of coordinates the question reduces to: which polynomials in $k[Y_1, \ldots, Y_n]$ vanish at $0$? Answer: those with zero constant term, i.e. those in the ideal $(Y_1, \ldots, Y_n)$.
Concretely, expand $\Phi f$ as a $k$-linear combination of monomials in $Y$:
\begin{align*}
(\Phi f)(Y) = \sum_\alpha c_\alpha Y^\alpha = c_0 + \sum_{|\alpha| \ge 1} c_\alpha Y^\alpha.
\end{align*}
Evaluating at $0$ leaves only $c_0$, which equals $f(a) = 0$. So every term in the sum has $|\alpha| \ge 1$, hence is divisible by some $Y_i$, hence lies in $(Y_1, \ldots, Y_n)$. Reversing the substitution,
\begin{align*}
f \in (X_1 - a_1, \ldots, X_n - a_n).
\end{align*}
\textbf{Conclusion of this step.} $\ker(\mathrm{ev}_a) = (X_1 - a_1, \ldots, X_n - a_n)$, and this kernel is a maximal ideal because $k[X_1, \ldots, X_n]/(X_1 - a_1, \ldots, X_n - a_n) \cong k$.[/guided]