Your equations imply
\begin{align*}
a + b = (1-p)(p+q) + (1-q)(p+q),
\end{align*}
maximising the function
$$
F(p,q) = (1-p)(p+q) + (1-q)(p+q)
$$
over the unit square, formally using Lagrangian multipliers or by heuristically guessing straight from symmetry this is maximised on the set $ p + q = 1$ and so
$$
a + b = F(p,q) \leq 1.
$$
Edit I have run out of time a little and I hope to come back to this but this is what I have so far for showing the equivalence in the other direction, it needs more work and also handling of the degenerate cases where $a$ or $b$ is equal to zero, I have posted it in the hope it will still help.
Let
$$
A = \begin{pmatrix}
1 - a & a \\
b & 1-b
\end{pmatrix}
$$
then we can we find the eigenvalue, eigenvector pairs
$$
\lambda_1 = 1,\; \; v_1 = 1
$$
and
$$
\lambda_2 = 1 - (a+b), \; \; v_2 = (-\frac{a}{b}, 1)
$$
so we can use the usual spectral decomposition to write $A$ as
$$
A = \mathbf{V}\mathbf{D}\mathbf{V}^{-1}
$$
now assuming $a+b \leq 1$ we have
\begin{align}
P &=
\begin{pmatrix}
1 & -\frac{a}{b} \\
1 & 1
\end{pmatrix}
\begin{pmatrix}
1 & 0 \\
0 & \sqrt{1 - (a+b)}
\end{pmatrix}
\begin{pmatrix}
1 & -\frac{a}{b} \\
1 & 1
\end{pmatrix}^{-1} \\
&=
\begin{pmatrix}
1 & -\frac{a}{b} \\
1 & 1
\end{pmatrix}
\begin{pmatrix}
1 & 0 \\
0 & \sqrt{1 - (a+b)}
\end{pmatrix}\frac{1}{a+b}
\begin{pmatrix}
b & a \\
-b & b
\end{pmatrix} \\
\end{align}
Working all this through gives
$$
\begin{bmatrix}
\frac{a}{a+b}\sqrt{1-(a+b)} + \frac{b}{a+b} &
\frac{a}{a+b} - \frac{a}{a+b}\sqrt{1-(a+b)}\\
\frac{b}{a+b} - \frac{b}{a+b}\sqrt{1-(a+b)} & \frac{b}{a+b}\sqrt{1-(a+b)} + \frac{a}{a+b}
\end{bmatrix}
$$
which after a bit of checking a tidying should be equivalent to a matrix of the form
$$
\begin{pmatrix}
p & 1 - p \\
1 - q & q
\end{pmatrix}.
$$