These questions has been asked many times here, but I was not able to find references in math.stackexchange with really complete answers. Perhaps somebody else will find something.
So let us do it again.
(a) You considered the map $f : \mathbb R \to S^1, f(x) = e^{2\pi i x}$. This is the right approach. In fact it is well-known that
$f$ is a surjective group homomorphism from the additive group $(\mathbb R, +)$ to the multiplicative group $(S^1, \cdot)$ of complex numbers with absolute value $1$.
The kernel of $f$ is the subgroup $\mathbb Z \subset \mathbb R$. In other words, $f(x) = f(y)$ iff $x - y \in \mathbb Z$.
$\mathbb R/\mathbb Z$ denotes the quotient of $\mathbb R$ modulo the subgroup $\mathbb Z$. Its elements are the cosets of $\mathbb Z$ in $\mathbb R$, i.e. the sets $[x]_{\mathbb Z} = x + \mathbb Z = \{x +k \mid k \in \mathbb Z\}$ with $x \in \mathbb R$. We have $[x]_{\mathbb Z} = [y]_{\mathbb Z}$ if and only if $x - y \in \mathbb Z$. Alternatively one can regard the elements of $\mathbb R/\mathbb Z$ as the equivalence classes $[x]_\sim$ of the points $x \in \mathbb R$ with respect to the equivalence relation defined by $x \sim y$ iff $x - y \in \mathbb Z$. Clearly $[x]_{\mathbb Z} = [x]_\sim$.
Let $p : \mathbb R \to \mathbb R/\mathbb Z, p(x) = [x]_{\mathbb Z}$, denote the canonical quotient map. This is both a topological quotient map to the quotient space $\mathbb R/\mathbb Z$ which is endowed with the quotient topology and an algebraic quotient map (i.e. a group homomorphism) to the quotient group $\mathbb R/\mathbb Z$.
$f$ induces a unique function $\bar f : \mathbb R/\mathbb Z \to S^1$ such that $\bar f \circ p = f$. It is well-known that $\bar f$ is continuous and a group isomorphism $\mathbb R/\mathbb Z = \mathbb R/\ker f \to \operatorname{im} f = S^1$. It remains to show that $\bar f$ is a homeomorphism. We know that it is continuous bijection. But clearly $\mathbb R/\mathbb Z = p([0,1])$, thus $\mathbb R/\mathbb Z$ is the continuous image of a compact set and therefore itself compact. This implies that $\bar f$ is a homeomorphism because $S^1$ is Hausdorff.
(b) Let $r : X \to Y$ be a quotient map between spaces $X,Y$. Define an equivalence relation $\sim_r$ on $X$ by $x \sim_r x'$ iff $r(x) = r(x')$. It is well-known that the induced map $\bar r : X/\sim_r \to Y$ (characterized by $\bar r \circ q = r$, where $q : X \to X/\sim_r$ is the standard quotient map) is a homeomorphism.
Now let $r = p \mid_{[0,1]} : [0,1] \to S^1$. This is a continuous surjection. Since $[0,1]$ is compact and $S^1$ is Hausdorff, it is a closed map and therefore a quotient map. The equivalence relation $\sim_r$ agrees with your $\sim$. Thus $\bar r : [0,1]/\sim \phantom . \to S^1$ is a homeomorphism.
Remark:
You could also use the method in (b) to prove (a). But it is somewhat more difficult to prove that $f$ is a quotient map. See here where it is shown that $f$ is an open map and therefore a quotient map.