The maximum principle for harmonic functions is actually based on a really simple and intuitive idea: for a harmonic function, the value of $V$ at a point $V$ is really just the average value that $V$ takes on neighboring points. This can be seen by looking at the problem on a lattice of points (let's stay in $2D$ for now). If we label our points as $x_{ij}$, then the first "derivative" looks like
$$\boldsymbol{\nabla}V=\frac{1}{a}\left(V(x_{i+1/2,j})-V(x_{i-1/2,j})\right)\hat{\textbf{x}}+\frac{1}{a}\left(V(x_{i,j+1/2})-V(x_{i,j-1/2}))\right)\hat{\textbf{y}}$$
(note that since this uses indices like $i\pm 1/2$, the gradient actually isn't well defined -- however, the Laplacian will be.) The "gradient" of this gives you the lattice Laplacian:
$$\nabla^2V=\frac{1}{a^2}\left(V(x_{i+1,j})+V(x_{i-1,j})+V(x_{i,j+1})+V(x_{i,j-1})-4V(x_{ij})\right).$$
Setting this equal to zero tells you that
$$V(x_{ij})=\frac{1}{4}\left(V(x_{i+1,j})+V(x_{i-1,j})+V(x_{i,j+1})+V(x_{i,j-1})\right),$$
so that $V(x)$ is really just an average of $V$ at neighboring points! This continues to hold in the $a\to 0$ limit, but let's stick with the discretized version to see what we can get.
Firstly, this argument shows very easily that a function which is harmonic on some domain $\Sigma$ must take its maximum on the boundary $\partial\Sigma$. If this weren't true, then it would have to be true that a point $x$ where $V(x)$ is maximal would have to be the average of points which are not maximal. That was easy! Applying the argument to $-V$ shows the same thing for the minima.
Secondly, it becomes very easy to show that solutions are unique. First, note that if a function is harmonic on $\Sigma$ and satisfies $V=0$ on $\partial\Sigma$, then $V=0$ everywhere on $\Sigma$. If not, then it would have its maximum on the interior of $\Sigma$, contradicting the above statement. Now, consider two harmonic functions $V_1$ and $V_2$ on $\Sigma$ which take the same values on the boundary $\partial\Sigma$. Then their difference $V_3=V_2-V_1$ is also harmonic and takes the value $V_3=0$ on the boundary. Thus, $V_3=0$ on $\Sigma$, so that $V_1=V_2$, showing that solutions are unique once boundary conditions are fixed. Thus, taking the continuum limit $a\to 0$, you are given your conclusions!
Another way to see this is to consider a point $x_0$ and then consider the average value of $V$ on a sphere of radius $R$ with $x_0$ at its center (let's take $x_0$ to be the origin for simplicity). This is given by
$$\frac{1}{4\pi R^2}\oint_{S_R}V(\textbf{x})\,\mathrm{d}S=\frac{1}{4\pi R^3}\oint_{S_R}(V(\textbf{x})\,\textbf{x})\cdot\mathrm{d}\textbf{S}=\frac{1}{4\pi}\oint_{S_R}V(\textbf{x})\frac{\textbf{x}}{|\textbf{x}|^3}\cdot\mathrm{d}\textbf{S}\\
=-\frac{1}{4\pi}\oint_{S_R}\boldsymbol{\nabla}\left(V(\textbf{x})\frac{1}{|\textbf{x}|}\right)\cdot\mathrm{d}\textbf{S}+\frac{1}{4\pi}\oint_{S_R}\frac{1}{|\textbf{x}|}\boldsymbol{\nabla}V(\textbf{x})\cdot\mathrm{d}\textbf{S}\\
=-\frac{1}{4\pi}\int_{B_R}\nabla^2\left(\frac{V(\textbf{x})}{|\textbf{x}|}\right)\mathrm{d}V,$$
where the second term in the second line vanishes by the divergence theorem and the fact that $\nabla^2V=0$. Now, noting that
$$\nabla^2\left(\frac{1}{|\textbf{x}|}\right)=-4\pi\delta(\textbf{x}),$$
and using traditional product rules for the Laplacian, we can obtain
$$\frac{1}{4\pi R^2}\oint_{S_R}V(\textbf{x})\,\mathrm{d}S=V(0),$$
which is a more rigorous derivation of the maximum principle.
I hope this helps!