For the sake of simplicity, let us consider the domain $X$ to be $\mathbb{R_+^n}$, and let $\succsim$be any preference relation(satisfying all the required choice axioms) on this domain.
Let $\textbf{x}$ and $\textbf{y}$ belong to the preference relation $\succsim$ (both $\textbf{x}$ and $\textbf{y}$ are points in $\mathbb{R_+^n}$), such that $\textbf{x}$$\succsim$$\textbf{y}$. This implies that there exists some utility representation $U$ of this relation, such that $\forall$ $\textbf{x}$,$\textbf{y}$$\in$$\mathbb{R_+^n}$, we have $U(\textbf{x})$$\geq$$U(\textbf{y})$. Now, if we consider any monotonically increasing function $f(.)$, then the former inequality can very well be written as $f(U(\textbf{x}))$$\geq$$f(U(\textbf{y}))$, $\forall$ $\textbf{x}$,$\textbf{y}$$\in$$\mathbb{R_+^n}$.
Coming back to your question, there can be two cases. If it is already known that $U$ and $U'$ induce the same preference relation on $X$, then all the assumptions are covered under the standard choice axioms. However, to prove that one is a monotonic transformation of the other(let's say $U'$ is a monotonic transformation of $U$) you can simply find out the demand correspondences corresponding to the two utility functions, and show that they are essentially the same. To see that this is true, consider the lagrangian $L$$=$$f(U(\textbf{x}))$ + $\lambda$$(w -\textbf{p.x}) $, where $w$$\in$$\mathbb{R_+}$ and $\textbf{p}$$\in$$\mathbb{R_+^n}$, and $f(.)$ is a monotonically increasing function as assumed earlier(you can also replace $f(.)$ with $U'(.)$, it's essentially the same thing). Taking the first order conditions, we get $f_U(U(\textbf{x})).U_{x_i}(\textbf{x}) -\lambda.p_{x_i}= 0$. Now, for any $i,j$$\in$ $\{1,2,..,n\}$, we have $f_U(U(\textbf{x})).U_{x_i}(\textbf{x})/p_{x_i}$$=$$f_U(U(\textbf{x})).U_{x_j}(\textbf{x})/p_{x_j}$, or $U_{x_i}(\textbf{x})/p_{x_i}=U_{x_j}(\textbf{x})/p_{x_j}$, which is the same condition that we would've obtained if the utility function was only $U(.)$. Thus, in layman language, the demand correspondences are exactly the same 'algebraic expressions' for $f(U(.))$ and $U(.)$.
The second case can be when you are not aware of any preference relation, you're just given two functions, $U \& U'$. In that case, you can similarly proceed to solve the Lagrangian, and check whether the expressions(read as solutions for all $x_i$) obtained are same or not. If they are not same, then neither of the two functions can be represented as a monotonic transformation of the other. If they are same, you'll still need to prove that the 'expression' obtained represents a demand correspondence, and hence a preference relation exists for the given utility functions. To prove that, you simply need to check whether the demand correspondences obtained satisfies all the properties pertaining to the Slutsky's matrix(you can refer to MWG for this section).