The state space of a qubit $\mathscr H\simeq \mathbb C^2$ is two-dimensional. The Pauli matrices $\{\sigma_i\}_{i=0,\ldots,3}$ form a basis for the real vector space of hermitian $2\times2$ matrices of dimension $2^2=4$, cf. e.g.this and the links therein. As such, any hermitian matrix can be expanded in this basis set.
A density operator is a positive operator (and hence hermitian) of unit trace and you can thus expand it in the basis of Pauli matrices:
$$ \rho = \sum\limits_{i=0}^3 r_i \, \sigma_i \quad , \tag{1}$$
with $r_i \in \mathbb R .$
Now use the positivity and trace condition to find conditions for the expansion coefficients. For example, you can write $\rho$ in a the basis of eigenvectors of $\sigma_3$ and diagonalize it. Then you'll see that $\rho$ is a density matrix if and only if
$$r_0=\frac{1}{2}\quad \text{and}\quad\sum\limits_{i=1}^3 r_i^2 \leq \frac{1}{4} \tag{2} $$holds.