- No. Neither Riemann integrable nor Lebesgue integrable functions need to be piecewise continuous. See the Thomae function.
- Yes. $L_2[-\pi,\pi] \subset L_1[-\pi,\pi]$, and the Fourier transform is defined for any element of $L_1$. (Note: $L_2(\mathbb R) \not\subset L_1(\mathbb R)$, so this argument does not work there. As mathreader said, the Plancherel transform extends the Fourier transform to $L_2(\mathbb R)$.)
Proof for $L_2[-\pi,\pi] \subset L_1[-\pi,\pi]$. Let $f \in L_2[-\pi,\pi]$.
Note $|f(x)| \le |f(x)|^2 + 1$, which we can see by considering the two cases $|f(x)|\le 1$ and $|f(x)| > 1$. So
$$
\int_{-\pi}^{\pi} |f(x)|\;dx \le \int_{-\pi}^{\pi} |f(x)|^2\;dx + 2\pi
< +\infty
$$
and $f \in L_1[-\pi,\pi]$
- No. $f(x) = 2+\sin x$ is smooth on $\mathbb R$, but $f$ is not in $L_1(\mathbb R)$.