The phrase "postulating" might be a bit misleading. Often, the iterated integrals (the second order process) are defined in some canonical way. Besides, all rough path lifts differ by the increment of a function.
Lemma: Let $(X,\mathbb X)$ and $(X,\tilde{\mathbb X})$ be two $\gamma$-rough paths. Then there is some $F\in C^{2\gamma}$ so that $\mathbb X_{s,t}=\tilde{\mathbb X}_{s,t}+F(t)-F(s).$
Proof: Chen's relation says that $\mathbb X_{s,t}-\mathbb X_{s,u}-\mathbb X_{u,t}=\tilde{\mathbb X}_{s,t}-\tilde{\mathbb X}_{s,u}-\tilde{\mathbb X}_{u,t}$ for all $s,u, t.$ Defining $F_{s,t}=\mathbb X_{s,t}-\tilde{\mathbb X}_{s,t}$ shows that $F_{s,t}-F_{s,u}-F_{u,t}=0$ or $F_{s,t}=F_{s,u}+F_{u,t}$. Chen's relation also implies that $F_{s,u}=-F_{u,t}$. So $F_{s,t}=F_{u,t}-F_{u,s}$. Also, $F\in C^{2\gamma}$ because $\mathbb X,\tilde{\mathbb X}$ are. Define $F(t):=F_{u,t}$.
Note crucially that in general $F$ cannot be a smooth function of $X$. If $F(t)=\phi(X(t))$ for smooth $\phi$ then $F(t)-F(s)=\phi'(X(s^\ast))(X(t)-X(s))$ by the mean value theorem. So you should expect no more regularity from $F$ than from $X$. For example Ito and Stratonovich differ by $F(t)=\frac12 t$.
This is reminiscent of standard calculus. If you have a continuous function $f$ then you can ``postulate" any antiderivative $F$ you want, so long as it satisfies $F'=f$. There are infinitely many choices. However given any $F_1,F_2$ that satisfy $F_1'=F_2'=f$, we have that $F_1-F_2=C$ for some constant $C$.
One way of stating this is in terms of a ``difference" operator $\delta$. Let $V$ be a vector space. Given a function $F:[0,1]\to V$ we can define $\delta F:[0,1]^2\to V$ by $\delta F_{s,t}=F(t)-F(s)$. Furthermore, if $F:[0,1]^2\to V$ we define $\delta F:[0,1]^3\to V$ by $\delta F_{s,u,t}=F_{s,t}-F_{s,u}-F_{u,t}$.
With this difference operator we have that $\delta F_{s,t}=0$ iff $F$ is constant and $\delta F_{s,u,t}=0$ iff $F=\delta G$ for some $G:[0,1]\to V$.
The point I am making is that you can't write down ``whatever you want" - in practice it is quite hard to explicitly construct natural rough paths above various signals.
What happens in practice is that you take a natural smooth approximation of $X$, call it $X^\varepsilon$. You construct the Riemann-Stieltjes integrals above $X^\varepsilon$ and you hope that this pair converges in the rough topology. Sometimes it does sometimes it doesn't. When it does converge, such limiting rough paths are called ``geometric."