The proof is essentially a generalisation of the $5$-Colour Theorem:
Proof. Consider the set $S$ of planar graphs which are not $4$-colourable. Choose the graph $G \in S$ that has the least number of vertices. If there are multiple such graphs let $G$ denote any one of these arbitrary graphs.
Since $G$ is planar, there exists a vertex $v$ in $G$ such that $deg(v) \leq 5$. Suppose that $deg(v) = 5$; the case $deg(v) = 4$ will follow from this result. If $deg(v) \leq 3$ the result is almost trivial.
Denote the adjacent vertices of $v$ by $x_1, x_2, ..., x_5$. By hypothesis, removing any vertex from $G$ makes the subsequent graph $4$-colourable. As a result, we can colour $G \setminus \{v\}$ with four colours and append $v$ (uncoloured) back afterwards. Since we've just used four colours on the five adjacent $x_i$, it follows that least two must be same colour, say $x_1, x_2$.
We now consider $v, x_2, ..., x_5$ (omitting one of the same-coloured vertices we've just found above). If the remaining $x_i$ are all required to be different colours then there must exist a path between each $x_i, x_j$ with the vertices on this path alternating through the respective colours, otherwise either one of the $x_i, x_j$ can change its colour to match the other. However, as seen in the diagram below, this would contradict the planarity of the graph $G$, which in turn implies that that two of the remaining $x_i$ can indeed share a colour after all.
In the diagram above $x_3$ can share the same colour as $x_5$ since they cannot be connected by any path of alternating colours without violating planarity. In this case we then get that $x_1, x_2$ share the same colour (from earlier) and $x_3, x_5$ also share the same colour. The last adjacent vertex $x_4$ is coloured in the third colour, thus allowing $v$ to be coloured in a fourth, providing the necessary contradiction.
However, the diagram above only illustrates one of two possible scenarios. Suppose that again $x_1, x_2$ share the same colour to begin with. Then we omit $x_1$ again, but this time $x_2$ shares colour with one of $x_3, x_4, x_5$ (instead of $x_3$ and $x_5$ as in the diagram above). Then we get that $x_1, x_2, x_3$ all share the same colour, $x_4$ is coloured in the second colour, $x_5$ is coloured in the third colour leaving $v$ to be coloured in the fourth, providing the contradiction again.
Where've I gone wrong?
The proof turns out to be the same as the one provided by Alfred Kempe in 1879. The subtle oversight is that the same-coloured vertex which we first find (namely $x_1$) can in fact turn out to be neighbouring two of the other vertices we deal with in Case 2 above, causing a problem when trying to reduce the adjacent vertices to three colours at the end (as pointed out in a counterexample provided by Percy J. Heawood in 1890).