Briefly, let $W^+$ denote the positive spin bundle of the given $Spin_c$- structure so that $det(W^+)=L$. Then the condition
$
c_1^2(L)=2\tau(M)+3\sigma(M)
$
is equivalent, using a little characteristic class magic, to
$
c_2(W^+)=0.
$
The latter means (on a 4-manifold) that $W^+$ admits a non-vanishing section $\Phi$ which WLOG has unit length. Clifford multiplication against this $\Phi$ induces a real isomorphism
$
\theta \in T^{*}M \mapsto c(\theta)\Phi \in W^-
$
so the cotangent bundle inherits being a complex vector bundle from the complex vector bundle $W^-$ and hence $M$ an almost complex structure.