  For three-dimensional (3D) crystalline insulators, preserving space-inversion
($\mathcal{P}$) and time-reversal ($\mathcal{T}$) symmetries, the third
homotopy class of two-fold, Kramers-degenerate bands is described by a 3D
winding number $n_{3,j} \in \mathbb{Z}$, where $j$ is the band index. It
governs space group symmetry-protected, instanton or tunneling configurations
of $SU(2)$ Berry connection, and the quantization of magneto-electric
coefficient $\theta_j = n_{3,j} \pi$. We show that $|n_{3,j}|$ for realistic,
\emph{ab initio} band structures can be identified from a staggered
symmetry-indicator $\kappa_{AF,j} \in \mathbb{Z}$ and the gauge-invariant
spectrum of $SU(2)$ Wilson loops. The procedure is elucidated for $4$-band and
$8$-band tight-binding models and \emph{ab initio} band structure of Bi, which
is a $\mathbb{Z}_2$-trivial, higher-order, topological crystalline insulator.
When the tunneling is protected by $C_{nh}$ and $D_{nh}$ point groups, the
proposed method can also identify the signed winding number $n_{3,j}$. Our
analysis distinguishes between magneto-electrically trivial ($\theta=0$) and
non-trivial ($\theta=2 s \pi$, with $s \neq 0$) topological crystalline
insulators. In Part II, we demonstrate $\mathbb{Z}$-classification of $\theta$
by computing induced electric charge (Witten effect) on magnetic Dirac
monopoles.
