I'm having a confusion with understanding the equality of rvs.
If $X \sim Exp(1)$ and $Z=2X$, then $Z \sim Exp(\frac{\lambda}{2})$. If also $Y \sim Exp(1)$, then $X$ and $Y$ are iid and $Z=X+Y, Z \sim Erlang(2,1)$. I don't quite understand the case when, for example, $Z=X+X$, or (equivalently?), $Z=X+Y$ when $Y=X$, because I don't fully understand what it means for two rvs to be $equal$.
From the axiomatic point of view, if $\exists$ probability triple $(\Omega, \mathcal{F}, P)$ with two measurable functions $X,Y$ defined on this triple, for these two measurable functions ('random' 'variables') to be equal is to have $X(\omega)=Y(\omega) \ \forall \omega: X,Y \subset \mathbb{R}$ except maybe $\omega$ with Lebesgue measure $0$. The strict inequality, e.g. $X_n(\omega)<X(\omega) \ \forall \ n$ is then used for proving sure/almost sure convergence of rvs.
I don't quite understand how to apply the equality in axiomatic sense to the problem above, e.g. finding the distribution of $Z=X+X$ and $Z=X+Y$.
This only addresses the "...I don't fully understand what it means for two rvs to be equal" part of your question.
Random variables are functions.
Two random variables $Y_1:(\Omega,\mathscr{F},P)\rightarrow\mathbb{R}$ and $Y_2:(\Omega,\mathscr{F},P)\rightarrow\mathbb{R}$ are equal od $Y_1(\omega)=Y_2(\omega)$ for all $\omega\in\Omega$. In shuch case, the also have the same distribution.
It could be that two random variables are define in the same probability space, they are not equal and yet, they have the same distribution: $$X_1:((0,1),\mathscr{B}(0,1),\lambda)\rightarrow\mathbb{R}$$ defined by $$X_1(t)=\mathbb{1}_{(0,1/2]}(t)$$ and $$X_2:((0,1),\mathscr{B}(0,1),\lambda)\rightarrow\mathbb{R}$$ defined by $$X_2(t)=\mathbb{1}_{(1/2,1)}$$ where $\lambda$ is the probability measure on $(0,1)$ that assigns to any subinterval $(a,b]\subset(0,1)$ it length: $\lambda((a,b])=b-a$.
Clearly $X_1\neq X_2$. However, since
$$\begin{align} P[X_1=1]&=\lambda(\{t: X_1(t)=1\})=\lambda((0,1/2])=1/2\\ P[X_2=1]&=\lambda(\{t: X_2(t)=1\})=\lambda((1/2,1))=1/2 \end{align} $$ and both $X_1$ and $X_2$ take values $0$ or $1$, we have that $X_1\stackrel{law}{=}X_2$, that is, they have the same distribution.
$$Z_1:((0,1)\times(0,1),\mathscr{B}((0,1)\times(0,1)),\lambda_2)\rightarrow\mathbb{R}$$ defined by $$Z_1(s,t)=s$$ and $$Z_2:((0,1),\mathscr{B}((0,1)),\lambda)\rightarrow\mathbb{R}$$ defined by $$Z_2(x)=x$$
where $\lambda_2$ is the measure that assigns to each box in $(0,1)\times(0,1)$ it area.
$Z_1$ and $Z_2$ are random variables defined in different probability spaces; but $$\lambda_2(a<Z_1\leq b)=\lambda_2((a,b]\times(0,1))=b-a=\lambda_2(a<Z_1\leq b)$$ Thus, $Z_1\stackrel{law}{=}Z_2$.