I am not sure if my approach is on the right track for $\Rightarrow$, since I don't know how to proceed and reach the conclusion that $A$ meets each path-component of $X$? And I hope my approach to the other direction make sense?
$H_0(X,A) = 0 \iff A$ meets each path-component of $X$.
By Theorem 2.16, we have the exact sequence:
$$\cdots H_0(A) \stackrel{i_*}{\to} H_0(X) \stackrel{j_*}{\to} H_0(X,A) \to 0$$
$\Rightarrow$: If $H_0(X, A) = 0$, then $H_0(X) = \ker j_*(H_0(X)) = \operatorname{Im}i_*(H_0(A))$. Because $H_0(X) = \operatorname{Im}i_*(H_0(A))$, we know $i_*$ is surjective.
Edit: I hope I figured this out?
The map $i_*: H_0(A) \to H_0(X)$ is surjective implies that the map $i_*: \bigoplus_\alpha H_0(A_\alpha) \to \bigoplus_\beta H_0(X_\beta)$ is surjective. That is to say that $\forall \beta, \exists A_\alpha : i(A_\alpha) \subset X_\beta$. Hence $A$ meets each path-component of $X$.
$\Leftarrow$: According to Proposition 2.7, for any space $X$, $H_0(X)$ is a direct sum of $\mathbb{Z}$'s, one for each path-component of $X$. So if $A$ meets each path-component of $X$, $H_0(X) = H_0(A) \approx \mathbb{Z}$. So the inclusion $i: A \to X$ induces a surjection $H_0(A) \to H_0(X)$.
So since $H_0(A) \to H_0(X)$ is surjective, $\operatorname{Im} i_*(H_0(X)) = H_0(X, A) = \ker H_0(X, A)$. Since the entire $H_0(X, A)$ lies in the kernel of $j_*$, $H_0(X, A) = 0$.