My knowledge of $C^*$-algebras is very little.
We call an element positive if $a=b^*b$ for some $b$ and make a relation on all positive elements by saying $$ b \geqslant a \iff b-a \text{ is positive}. $$ I can't figure out why this gives us a poset.
Only anti-symmetry seems to be non-trivial here. Let us apply the spectral theorem.
Suppose that $b\leqslant a$ and $a\leqslant b$. Since $a-b$ is positive, $C^*(a-b)$ is commutative and of course $b-a\in C^*(a-b)$. But now you can think of $a-b$ and $b-a$ as continuous functions on $\sigma(a-b)$ which are both positive (non-negative, strictly speaking). Since $a-b = -(b-a)$, necessarily $a-b=0$.