We can express any such matrix as
$$
\pmatrix{
a_{11} & a_{12} & 1 - a_{11} - a_{12}\\
a_{21} & a_{22} & 1 - a_{21} - a_{22}\\
1 - a_{11} - a_{21} & 1 - a_{12} - a_{22} & a_{11} + a_{12} + a_{21} + a_{22} - 1
}
$$
From the discussion in the comments: why is this parameteriation a "good description" of the set? As soon as you know those four parameters, all other entries are forced. On the other hand, for any combination of values for those parameters, there's a valid matrix. That is, our parametrization over $\Bbb R^4$ is both injective and surjective.