Burnside's Lemma states that the number of orbits $|X/G|$ of a set $X$ under the action of a group $G$ is given by:
\begin{equation}
|X/G| = \frac{1}{|G|}\sum_{g \in G}|X^g|
\end{equation}
where $X^g$ denotes the set of elements in $X$ fixed under the action of $g$.
For the example given, your set $X$ is all the possible ways to arrange three different coloured plates around a square table and $G$ is the set of rotations of the square.
You can think of an arrangement as a string of length four, e.g. the string $RRWB$ indicates the first plate is red, the plate opposite is white, etc. There are $3^4$ arrangements of this kind, so we expect our answer to be smaller than this as, for instance,
$RRWB,RWBR,WBRR \text{ and } BRRW$ are all considered to be equivalent as each may be obtained from another by rotation.
We say that the set $\{RRWB, RWBR, WBRR, BRRW\}$ is the orbit of the element $RRWB \in X$ under $G$, and the orbit of $X$ is the set of orbits of each element $x \in X$.
Now, $G$ contains $4$ elements which are rotation by $0,90,180 \text{ and } 270$ degrees respectively. Clearly, all elements in $X$ are fixed under rotation by $0$ rads, so $|X^0|=|X|=3^4$.
The arrangements fixed under rotation by $90$ degrees require that each plate be the same colour as the one next to it and thus include $RRRR,WWWW$ and $BBBB$ only. By symmetry, $$|X^{90}|=|X^{270}|=3$$
A similar counting argument shows that $|X^{180}|=3^2$ and thus by Burnside's Lemma:
$$|X/G|=\frac{1}{4}\left( |X^0|+|X^{90}|+|X^{180}|+|X^{270}|\right) $$
$$~~ = \frac{1}{4}(81+3+9+3)=\frac{96}{4}=24$$