[step:Characterise $v \sim w$ as the existence of a combinatorial edge path]
Let $E_K$ denote the set of oriented $1$-simplices of $K$, and for an oriented edge $e = \langle v, w \rangle$ let $e^{-1} := \langle w, v \rangle$ denote the opposite orientation. On $1$-chains, $d_1$ acts linearly and satisfies $d_1 \langle v, w \rangle = w - v$ and hence $d_1 \langle w, v \rangle = v - w = -d_1 \langle v, w \rangle$, so reversing orientation reverses the sign.
[claim:$v \sim w$ if and only if there is an edge path from $v$ to $w$ in $K$]
We prove both directions.
($\Leftarrow$) Suppose there is an edge path from $v$ to $w$, that is, a sequence of vertices $v = v_0, v_1, \ldots, v_k = w$ with $\langle v_{i-1}, v_i \rangle \in E_K$ or $\langle v_i, v_{i-1}\rangle \in E_K$ for each $i$. For each $i$, choose an oriented edge $e_i \in E_K$ with endpoints $\{v_{i-1}, v_i\}$; define $\varepsilon_i = +1$ if $e_i = \langle v_{i-1}, v_i \rangle$ and $\varepsilon_i = -1$ if $e_i = \langle v_i, v_{i-1} \rangle$. Set
\begin{align*}
c := \sum_{i=1}^k \varepsilon_i e_i \in C_1(K).
\end{align*}
We verify the identity $\varepsilon_i \, d_1 e_i = v_i - v_{i-1}$ in both cases. If $e_i = \langle v_{i-1}, v_i \rangle$ then $\varepsilon_i = +1$ and $d_1 e_i = v_i - v_{i-1}$, so $\varepsilon_i d_1 e_i = v_i - v_{i-1}$. If $e_i = \langle v_i, v_{i-1} \rangle$ then $\varepsilon_i = -1$ and $d_1 e_i = v_{i-1} - v_i$, so $\varepsilon_i d_1 e_i = -(v_{i-1} - v_i) = v_i - v_{i-1}$. In either case $\varepsilon_i d_1 e_i = v_i - v_{i-1}$. Therefore
\begin{align*}
d_1 c = \sum_{i=1}^k \varepsilon_i \, d_1 e_i = \sum_{i=1}^k (v_i - v_{i-1}) = v_k - v_0 = w - v,
\end{align*}
a telescoping sum. Hence $w - v \in \operatorname{im} d_1$, i.e. $v \sim w$.
($\Rightarrow$) Suppose $v \sim w$, so there exists $c \in C_1(K)$ with $d_1 c = w - v$. Write $c = \sum_{e \in E_K} n_e \, e$ with $n_e \in \mathbb{Z}$ and only finitely many nonzero. Define a formal edge path from $v$ to $w$ as follows: consider the multigraph $\Gamma$ on the vertex set $V_K$ with, for each oriented edge $e = \langle a, b \rangle \in E_K$, exactly $|n_e|$ unoriented edges between $a$ and $b$. We show $\Gamma$ connects $v$ to $w$.
For a vertex $u \in V_K$, let $\deg_\Gamma(u)$ denote the total number of edges of $\Gamma$ incident to $u$. Consider the coefficient of each vertex $u$ in $d_1 c = w - v$:
\begin{align*}
\text{coefficient of } u \text{ in } d_1 c = \sum_{e = \langle a, b\rangle \in E_K} n_e \left( \mathbb{1}_{\{b = u\}} - \mathbb{1}_{\{a = u\}} \right).
\end{align*}
By hypothesis this coefficient equals $+1$ if $u = w$, $-1$ if $u = v$, and $0$ otherwise (assuming $v \neq w$; if $v = w$ the claim is trivial). In particular, the sum of integer contributions at each $u \neq v, w$ vanishes, so the parity of $\deg_\Gamma(u)$ is even; similarly $\deg_\Gamma(v)$ and $\deg_\Gamma(w)$ have odd parity. By the standard Euler-path characterisation, a multigraph with exactly two odd-degree vertices admits a walk from one odd vertex to the other, so $\Gamma$ contains a walk from $v$ to $w$. Projecting this walk to $V_K$ gives an edge path in $K$ from $v$ to $w$.
[/claim]
[/step]