The theorem is precisely asserting the existence and uniqueness of binary expansions of any positive integer $n$. That's what the $c_j$'s are: the digits of the binary expansion.
I hope the previous paragraph answers your second question. As for the first: no, the $c_r$'s can be arbitrary elements of $\{0,1\}$, with the one constraint that the last one of them is $1$ (if they were all $0$ we would get $0$, not a positive integer; and since the expansion is finite there must be a last nonzero term). So for instance $(c_0,c_1,c_2,c_3,c_4) = (1,1,1,1,1)$ is the binary expansion of $1+2+4+8+16= 31$.