Simple connection is important in different areas of mathematics:
$real$ $analysis:$ if you have an exact $1$-form $\omega$ and you need to integrate it along a closed path $\gamma$ contained in a simple connected space then
$$\int_\gamma \omega =0$$
because $\gamma$ is homotopic to a point and the integral does not change over any path in the homotopy class of $\gamma$. Moreover by the statement above; if $\gamma_1,\gamma_2$ are two different paths starting and ending at same points, then
$$\int_{\gamma_1} \omega=\int_{\gamma_2}\omega.$$
$Covering$ $space:$ In algebraic topology every ''good enough'' topological space, I mean semi-locally simply connected, locally path connected admits a simply connected covering space.
$Riemann$ $Surfaces:$ If this beautiful area of math one of the most important theorem is the Uniformization Theorem: Every simply connected Riemann Surface is biholomorphic to only one of these three domains: the sphere, the complex plane or the upper half plane.
Complex Analysis: See the Monodromy on this page. https://en.wikipedia.org/wiki/Monodromy Simple connection is the crucial hyphotesis.