The way you interpret $k$ is a bit off: the condition is that
$$ u(x) \neq k\pi$$
for all $k\in \mathbb Z$ and $x\in [0,1]$. So you cannot split into two cases ($k=0$ and $k\neq 0$).
If $u\in A$, by the intermediate value theorem,
$$ u \in A_k = \{ u\in A : k\pi < u(x) < (k+1) \pi, \ \ \forall x\in [0,1]\}$$
for some $k\in \mathbb Z$, and $A$ is the disjoint union of $A_k$ for $k\in \mathbb Z$.
It is easy to show that the closure of $A_k$ is
$$\overline {A_k} = \{ u\in C^1[0,1] : |u'|\le 2, \ \ k\pi \le u(x) \le (k+1) \pi\}$$
By definition of $\partial A$, we need to find the interior $A^\circ $ of $A$. We claim that
$$\tag{1} A^\circ = \{ u\in A : |u'(x)| <2, \ \ u(x) \neq k\pi,\ \ \forall k\in \mathbb Z, x\in [0,1]\}.$$
The inclusion $\supset$ is clear. On the other hand, if $u\in A$ and is not in the right hand side of $(1)$. Then there is $x_0\in [0,1]$ so that $u'(x_0) = \pm 2$. Then for all $\epsilon >0$,
$$ u_\epsilon (x) = u(x) \pm \epsilon x$$
satisfies $u'_\epsilon (x_0) = \pm (2+\epsilon)$ Hence $u_\epsilon \notin A$. But clearly $\| u_\epsilon - u\| \le 2\epsilon$. Hence $u$ is not in $A^\circ$.
Finally, by definition of $\partial A = \overline A \setminus A^\circ$,
\begin{split} \partial A &= \{ u : |u'|\le 2,\ k\pi \le u(x) \le (k+1)\pi \ \ \forall x\in [0,1], \text{ for some } k\in \mathbb Z \\
&\ \ \ \ \ \ \ \ \text{and } \exists x_0\in[0,1] \text{ such that either } \\
&\ \ \ \ \ \ \ \ u'(x_0) = \pm 2 \text{ or } u(x_0) = k\pi \text{ or } u(x_0) = (k+1)\pi\}
\end{split}
The description is a bit complicate, but for example, $\partial A$ contains infinitely many constant functions $u(x) = k\pi$ (for all $k\in \mathbb Z$), and it also contains (e.g.) $u(x) = x^2$ and $u(x) = 2x$.