Suppose that, starting from a regular $n$-simplex with vertices labeled with $(v_1, v_2, \ldots v_n)$ I want to obtain an arbitrary permutation of the vertices $(w_1, w_2, \ldots w_n)$ out of the $n!$ possible, is it enough to:
- Rotate the $n$-simplex around its centroid till $w_i$ is in the position occupied by $v_i$, $i = 1, \ldots ,n$ in the original positioning of the $n$-simplex;
- If step 1. is not enough, exchange $v_1$ and $v_2$ in the original positioning and then repeat step 1. till $w_1$ replaces $v_2$, $w_2$ replaces $v_1$, and $w_i$ is in the position occupied by $v_i$, $i = 3, \ldots ,n$ in the original orientation of the $n$-simplex;
Regarding the rotation about the centroid, for 2D it is clear, for 3D I mean any sequence of single rotations of any angle around whatever axis passing by the centroid. For 4D or more, something similar... What I mean is I can move the solid provided that its integrity is preserved and the centroid stay still. After comments and answers, a more formal way to say this is apply a rigid motion fixing the centroid, or apply an orientation preserving isometry of the ambient space fixing the centroid.
Is this feasible?
The most straightforward thing to do is a sequence of up to $\binom n2$ reflections.
Assuming a regular $n$-simplex, we can draw a hyperplane through $n-2$ of the points, passing through the midpoint of the edge between the remaining $2$ points, and perpendicular to that edge. A reflection through that hyperplane swaps those $2$ points while keeping the rest fixed.
Since we can generate any permutation by a sequence of swaps, we can permute the vertices however we like by a sequence of reflections.
Indirectly, this method also confirms that a plan like the one you describe also works. The composition of two reflections is a rotation (through the $(n-2)$-dimensional "axis" where the two hyperplanes intersect). In this case, all of the hyperplanes above pass through the centroid, so the "axes" will also contain the centroid.
So just take a sequence of reflections that gives you the permutation you want, then group them up into consecutive pairs. This will give you a sequence of rotations, possibly with one reflection left over.
(I should clarify that I mean a simple rotation here. In 4-dimensional space is when this first matters: a "simple rotation" fixes a plane, and "double rotations" are weirder. For higher values of $n$, you get even more complexity, but the composition of two reflections is always a simple rotation.)