This group contains all permutations of 3 elements, so it has order 3!=6.
Its three congruency classes are {1}, {(1,2),(1,3),(2,3)}, {(123),(132)}. As we know that the number of congruency classes equals the number of irreducible characters, we know that there are 3 irreducible characters (of degrees, say, $a,b,c$, such that $a^2+b^2+c^2=6$).
The two most obvious representations are the trivial one and the sign one, both of degree 1. Hence $a=b=1$, and therefore $c=2$.
How can I find $c$? My book says to use the orthogonality relations (i.e. irreducible characters form an orthonormal system), but I don't really see how.
You have already find two representations and the dimension of the last one, so you have the table : $$\begin{array}{|c|c|c|c|} \hline & \text{Id} & (i,j) & (i,j,k) \\ \hline 1\!\!1 & 1 & 1 & 1 \\ \hline \epsilon & 1 & -1 & 1 \\ \hline \chi & 2 & \alpha & \beta \\ \hline \end{array}$$
Do you know why the first entry of the last row $\chi(\text{Id})=2$ ? Now, to find $\alpha$ and $\beta$, you can use the orthogonality of the columns. For example, we know that $(1,1,2) \cdot (1,-1,\alpha)=0$ so $2\alpha=0$.