Update 1: The answer to Question 2 is negative, as Geva Yashfe points out in the comments.
The main question now is:
IsQuestion 3: Is every CW-complex (or other nice space, see e.g. Ian Agol’s answer) which is an $n$-tree contractible? Simply-connected?
Update 2 The answer to Question 3 is negative: as Geva Yashfe points out, an annulus is a 2-tree.
A remaining question is:
Question 4: Is every $(n-1)$-connected CW-complex which is an $n$-tree contractible?
But here is another variant of the recurersive definition of n-tree that perhaps makes Q3 interesting again:
Definition 3:
$\bullet$ a point is a strong 0-tree;
$\bullet$ A space X is a strong n-tree, if for every two disjoint strong $(n-1)$-trees $T,T'$ in X, there is a strong $(n-1)$-tree $S$, disjoint from $T,T'$ that separates them.
Question 5: Is every strong $n$-tree contractible?
Going through the above examples and non-examples with 2-trees replaced by strong 2-trees is interesting.
My motivation goes back to a theorem of Manning, saying that a graph is quasi-isometric to a tree if (and only if) every two points $x,y$ are separated by a ball of uniformly bounded radius around any midpoint from $x$ to $y$. This could be reformulated as saying that $X$ is a quasi-1-tree iff every two disjoint strong quasi-0-trees in $X$ can be separated by a third strong quasi-0-tree disjoint from both. I'm looking for the right definition that will generalise this to higher dimensions. Thus I propose:
Question 6: Let $X$ be a geodesic metric space in which every two disjoint strong quasi-(n-1)-trees can be separated by a third strong quasi-(n-1)-tree disjoint from both. Then $X$ is a strong quasi-n-tree.
By strong quasi-n-tree here I mean a space quasi-isometric to a strong n-tree, and the constants are some function of the dimension and the constants used in dimension $n-1$.