Interesting question.
But, alas, the answer is no.
The issue is that you have missed an extra non-rationality criterion. Namely, it is possible that such a surface $X$ has $\mathrm{Br}(X) = \mathrm{Br}(k)$, yet we have $\mathrm{Br}(X_K) \neq \mathrm{Br}(K)$ for some finite extension $K/k$.
Problems of this type for cubic surfaces over finite fields are considered in the PhD thesis of Shuijing Li: http://arxiv.org/abs/0904.3555
Though she only works over finite fields, the analysis for surfaces over number fields with a cyclic splitting field is more-or-less identical.
Here is how the counter-example goes. Take your DP4 $X$ and blow it up in a rational point not on a line to obtain a cubic surface $S$. We then choose this surface so that it has conjugacy class $C_7$ in the notation of Manin's table (p176 of his book); such a surface exists over $\mathbb{Q}$ by the recent resolution of the inverse Galois problem for cubic surfaces by Elsenhans and Jahnel. Its splitting field is cyclic of order $6$.
You see from the table that the Brauer group of $S$ is constant. However this surface is non-rational. This is because the Brauer group (modulo constants) becomes $(\mathbb{Z}/2\mathbb{Z})^2$ after a cubic extension, as it becomes the class $C_3$ from Manin's table.
I don't know whether this more general "extra non-rationality criterion" I mention is sufficient over number fields. That it is sufficient over finite fields is proven in Theorem 5.3.7 in Li's thesis.
To approach this general problem over number fields, I guess one could just enumerate all conjugacy classes of subgroups of the appropriate Weyl group in magma, and study which Brauer groups arise as well as the configurations of lines, and use the non-rationality criterion given in Theorem 5.3.1 in Li.