First, a disclaimer - I know almost nothing about Lie Groupoids. I'm just following my nose and verifying each of the axioms.
In this post, we just want to show that $T^\ast G \rightrightarrows \mathfrak{g}^\ast$ is a groupoid. Later on, in another post, I'll worry about showing it's actually a Lie groupoid.
First, the objects of our category are elements of $\mathfrak{g}^\ast$, that is, they are linear functionals from $\mathfrak{g}$ to $\mathbb{R}$. (These only depend on the linear structure of $\mathfrak{g}$, not on the algebra structure). Also, to be clear, I'll be identifying $\mathfrak{g}$ with $T_e G$ where $e\in G$ is the identity. The morphisms are, by definition, elements of the cotangent bundle of $G$. That is, each morphism is nothing but a linear functional from $T_g G$ to $\mathbb{R}$.
Now, let $\theta:T_g G \rightarrow \mathbb{R}$ be any such functional. What is $s(\theta)$, the source of $\theta$? By definition, this should be an element of $\mathfrak{g}^\ast$. That is, it should map an element of $\mathfrak{g}$ to $\mathbb{R}$. The author tells you exactly how to do it. If $v\in\mathfrak{g}$, then $$s(\theta)(v) = \theta(d_e L_g (v)). $$ (Be careful, in general, $d_e L_g(v) \neq g+ v$ - often the right hand side doesn't even make sense!)
Notice that this is well defined: First, since both $d_e L_g$ and $\theta$ are linear maps, the composition is linear, so $s(\theta)$ is linear. Second, the map $d_e L_g :\mathfrak{g}\cong T_e G \rightarrow T_g G$, so the image of $d_e L_g$ lies in the domain of $\theta$, so we can compose them. Lastly, the domain of $d_e L_g$ is $T_e G\cong \mathfrak{g}$ and the range of $\theta$ is $\mathbb{R}$, so overall, $\theta \circ d_e L_g$ is really an element of $\mathfrak{g}^\ast$.
What is $t(\theta)$, the target of $\theta$? Again, this should be something linear which accepts in elements of $\mathfrak{g}$ and spits out real numbers. Once again, the author has already given us the formula: $$t(\theta)(v) = \theta(d_e R_g(v)).$$ Just as in the previous paragraph, one can check that this really is well defined.
Now, suppose $\theta \in T^\ast_g G$ and $\varphi\in T^\ast_h G$ are two morphisms and assume further that $t(\theta) = s(\varphi)$. In other words, that $$\theta \circ d_e R_g = \varphi \circ d_e L_h.$$ Using the fact that, for any $k\in G$, $d_k R_g$ and $d_k L_h$ are isomorphisms with inverses $d_{kg} R_{g^{-1}}$ and $d_{hk} L_{h^{-1}}$ respectively, and using the fact that the left and right multiplication commute (and thus, so do their differentials), we get the following chain of equalities: \begin{align} \theta \circ d_e R_g &= \varphi\circ d_e L_h\\ \theta \circ d_e R_g \circ (d_e L_h)^{-1} &= \varphi \\ \theta \circ d_e R_g \circ d_h L_{h^{-1}} &= \varphi \\ \theta \circ d_h(R_g \circ L_{h^{-1}}) &= \varphi \\ \theta \circ d_h(L_h^{-1}\circ R_g) &= \varphi \\ \theta \circ d_{hg} L_{h^{-1}} \circ d_h R_g &= \varphi \\ \theta \circ d_{hg}L_{h^{-1}} &= \varphi \circ (d_h R_g)^{-1} \\ \theta \circ d_{hg}L_{h^{-1}} &= \varphi \circ d_{hg} R_{g^{-1}}\end{align}
The composition of elements of $T^\ast G$ should be another element of $T^\ast G$ and the author tells you that $\theta \bullet \varphi = \theta \circ d_{hg}L_{h^{-1}}$ (which just happens to equal $\varphi \circ d_{hg}R_{g^{-1}}$.) Notice that this is just another element of $T^\ast G$. More specifically, $\theta \bullet \varphi \in T^\ast_{hg} G$.
Now that composition is defined, we need to check several things - that the operation is associative, that every point has a correspond identity morphism, and that every morphism is invertible.
Associativity. Given $\theta,\varphi,$ and $\eta$ with basepoints $g,h,$ and $k$ respectively, we have \begin{align} \theta \bullet (\varphi \bullet \eta) &= \theta \bullet (\varphi \circ d_{kh} L_{k^{-1}}) \\ &= \theta \circ d_{khg}L_{(kh)^{-1}} \\ &= \theta \circ d_{khg}(L_{h^{-1}} L_{k^{-1}}) \\ &= \theta \circ d_{hg}L_{h^{-1}}\circ d_{khg} L_{k^{-1}}\\ &= (\theta \circ d_{hg}L_{h^{-1}})\bullet \eta \\ &= (\theta \bullet \varphi) \bullet \eta \end{align}
Identity. Given $f\in \mathfrak{g}^\ast$, we seek an element $\theta \in T^\ast G$ to act as the identity morphism at $f$, meaning $s(\theta) = t(\theta) = f$. Well, we can think of $\mathfrak{g}^\ast$ as $T_e^\ast G$, so this gives a natural guess for $\theta$: pick $\theta = f\in T_e^\ast G$. Then $s(\theta) = \theta \circ d_e L_e = \theta = f$ and likewise for $t(\theta)$. We also have $\theta \bullet \varphi = \varphi \circ d_h R_{e^{-1}} = \varphi$ and likewise for compositions on the other side.
Inverses. Given a morphism $\theta\in T_g^\ast G$ we want to find an inverse. I claim that $\varphi\in T_{g^{-1}}^\ast G$ with $\varphi = \theta \circ d_{g^{-1}} L_{g^2}$ does the trick. First, note that $\theta \bullet \varphi = \theta \circ d_e L_g$ is a linear map from $\mathfrak{g}^\ast$ to $\mathbb{R}$, that is, it's the identity at the point $\theta\circ d_e L_g \in \mathfrak{g}^\ast = s(\varphi)$. Likewise, composition in the other order works as well.
All this just verifies we actually have a groupoid.