Let me expand slightly Dtseng comment. I will actually try to emphasize the geometric picture, rather than the blind application of formulae. The morphism $\phi\colon S\to \Bbb{P}^2$ is constructed via the sections of the line bundle $\mathcal{O_S}(C)$, which has $3$ independent sections, by Riemann-Roch. But this, I guess, you already know :)
With respect to this morphism, lines in $\Bbb{P}^2$ correspond to divisors in $|C|$. Now consider a point $p\in\Bbb{P}^2$ and two lines $\ell_1,\ell_2$ intersecting at $p$. Suppose $\ell_1$,$\ell_2$ correspond to $C_1,C_2\in|C|$. Where do $C_1$ and $C_2$ intersect? Well, $C_1\cdot C_2 = C^2=2$. This means that they intersect at two distinct points $x,y$ of $S$, at least for a generic choice of $p$, i.e. outside some closed Zariski subset $\Delta\subset\Bbb{P}^2$. Now before going on to determine what $\Delta$ actually is (the sextic curve), notice that we just proved $\phi$ to be generically $2$-to-$1$, i.e. a morphism of degree $2$.
Now let $\ell$ be the line corresponding to $C$ itself. By restricting $\phi$ we get a morphism of degree $d=2$
$$f\colon C\to\ell$$
Riemann-Hurwitz: $2g(C)-2=d(2g(\ell)-2)+r$, where $r$ is the degree of the ramification, i.e. the number of points of $\ell\cap\Delta$, but counted with multiplicity of course, so that more precisely
$$r = \ell\cdot\Delta \quad (= \deg\Delta)$$
Of course plugging all in the Riemann-Hurwitz formula we just get $r=6$, so $\Delta$ is a sextic. The fact that it is smooth is because $S$ is smooth (in general, the singularities of a double covering $S\to S'$ between two surfaces are precisely along the singular points of the ramification locus). I hope this helps a bit.