In fact, suppose merely that $\alpha$ is piecewise $C^1$. Let $v=\alpha’$ be “the” velocity of $\alpha$; this is piecewise continuous (it’s not necessarily defined at the vertices, but that doesn’t matter, assign it whatever value you wish there). Due to density of $C^{\infty}([a,b])$ in $L^1([a,b])$, there exists a sequence of $C^{\infty}$ maps $\beta_j:[a,b]\to\Bbb{R}^n$ such that $\|v-\beta_j\|_{L^1([a,b])}\to 0$ as $j\to\infty$. Now, define $\gamma_j:[a,b]\to\Bbb{R}^n$ as $\gamma_j(t)=\alpha(a)+\int_a^t\beta_j(s)\,ds$, which is smooth. Then, by the FTC and triangle and reverse-triangle inequality, we have for each $s\in [a,b]$,
\begin{align}
|\gamma_j(s)-\alpha(s)|+ \left|L(\gamma_j)-L(\alpha)\right|&=\left|\int_a^s(\gamma’(t)-\alpha’(t))\,dt\right|+\left|\int_a^b|\gamma_j’(t)|\,dt-\int_a^b|\alpha’(t)|\,dt\right|\\
&\leq \int_a^b|\gamma_j’(t)-\alpha’(t)|\,dt+\int_a^b\left||\gamma_j’(t)|-|\alpha’(t)|\right|\,dt\\
&\leq 2\int_a^b|\gamma_j’(t)-\alpha’(t)|\,dt\\
&=2\int_a^b|\beta_j(t)-v(t)|\,dt,
\end{align}
So, taking the supremum over all $s\in [a,b]$, we see that
\begin{align}
\|\gamma_j-\alpha\|_{C^0([a,b])}+|L(\gamma_j)-L(\alpha)|\leq 2\|\beta_j-v\|_{L^1([a,b])}.
\end{align}
By hypothesis, this last term vanishes as $j\to\infty$. Thus, we found a sequence of smooth curves $\gamma_j$ which converge to $\alpha$ uniformly, and such that their arclengths approach that of $\alpha$.
Note that due to continuity of $\alpha$, the FTC can be applied to it. Also, we added $\alpha(a)$ as the constant of integration to $\gamma_j(t)$’s definition so that both $\alpha$ and $\gamma_j$ have the same starting point (hence justifying our very first equal sign).
If you don’t want to appeal to this standard density result, then we can be more hands-on as follows. It suffices to consider only one vertex (the general case follows by induction). Hence, we may suppose that $v:[a,b]\to\Bbb{R}^n$ is such that for some $c\in (a,b)$, which WLOG we may take to be $c=0$, we have $v|_{(a,0)}$ and $v|_{(0,b)}$ extend to smooth functions on open neighbourhoods of $[a,0]$ and $[0,b]$ respectively.
Now, let $\phi_{\delta}:[a,b]\to\Bbb{R}$ be a smooth bump function taking values in $[0,1]$, and such that it is identically $0$ on $[-\delta,\delta]$ and identically $1$ outside $[-2\delta,2\delta]$. Then, the function $\beta_{\delta}=\phi_{\delta}\cdot v$ will be smooth on $[a,b]$, and
\begin{align}
\int_a^b|\beta_{\delta}(t)-v(t)|\,dt&=\int_a^b|\phi_{\delta}(t)-1||v(t)|\,dt\leq\|v\|_{\infty}\int_{-2\delta}^{2\delta}|\phi_{\delta}(t)-1|\,dt\leq \|v\|_{\infty}\cdot (1+1)\cdot (4\delta).
\end{align}
The $1+1$ is because $|\phi_{\delta}-1|\leq |\phi_{\delta}|+1\leq 1+1$. Hence, as $\delta\to 0$ this vanishes, showing that we found a sequence of smooth functions which converge to $v$ in the $L^1([a,b])$-norm.