Use \\[3ex]
for adding vertical space. But, in this case, you can even do better: if you notice, the matrices are not perfectly aligned to each other. So I propose a slightly different solution:
\documentclass{article}
\usepackage{amsmath,amssymb}
\newcommand{\C}{\mathbb{C}}
\newcommand{\Aaa}{%
\begin{bmatrix}1&0\\0&-1\end{bmatrix}%
}
\newcommand{\Ba}{%
\begin{bmatrix}0&1\\-1&0\end{bmatrix}%
}
\begin{document}
% Simplistic solution with `\\[3ex]`
\begin{displaymath}
\rho_1: V_{24}\longrightarrow GL_2(\C):
\begin{cases}
a\longmapsto \Aaa\\[3ex]
b\longmapsto \Ba
\end{cases}
\end{displaymath}
%% Better solution with horizontal alignment
\begin{displaymath}
\rho_1: V_{24}\longrightarrow GL_2(\C):
\begin{cases}
\begin{aligned}
a&\longmapsto \Aaa\\
b&\longmapsto \Ba
\end{aligned}
\end{cases}
\end{displaymath}
\end{document}
In the second solution, not only aligned
puts the two matrices one over each other, but it also succeeds to leave some vertical space between the rows, without explicit spacing.
