Let's start with question 2, because it's easier.
In one sense, an angle between two line segments in higher dimensions does make sense, because the two line segments (typically) form a two-dimensional plane. We can always embed a plane in $\Bbb{R}^n$ (or any real inner product space) into $\Bbb{R}^2$ isometrically, by choosing any orthonormal basis and mapping it to the standard basis of $\Bbb{R}^2$ linearly. The angle from the dot product formula will agree with the angle in the embedding, in the classic Euclidean sense (because linear isomorphisms preserve inner products, as well as norms).
In another sense, it makes more sense really to define an angle in terms of the inner product on the space. This way, we can define angles on more abstract inner products, e.g. on spaces of functions, and get an excellent concept of angles. The Cauchy-Schwarz inequality shows that $\cos^{-1} \frac{u \cdot v}{\|u\| \|v\|}$ is always well-defined, and given the previously mentioned isoometry property, we can even expect angle sums of triangles to be $\pi$, and other nice Euclidean properties.
The first question is the stickier one. I could respond with a simple "why not?"; we can define whatever we like, however we like. The dot product just so happens to be useful when we define it like that.
I could also choose to interpret your entire question as a request for an intuition about why a simple sum of products could say something so fundamental about angles. Intuition can always be a little tricky, because it is ultimately an individual response that others may not respond to, but here's where my intuition on the topic lies.
Fix a non-zero vector $u$ and an angle $\alpha \in (0, \pi)$. Consider two sets (picture them in $\Bbb{R}^3$): the unit sphere $S_X = \{x : \|x\| = 1\}$, a hollow cone consisting of all the vectors whose angle with $u$ is $\alpha$ (as well as $0$, the cone's vertex). The cone originates at the sphere's centre, so there's definitely going to be an intersection. What shape is this intersection?
In $\Bbb{R}^3$, it will be a circle laid on the sphere. On the cone, the circle will be an orthogonal cross-section. In higher dimensions, it will be a lower-dimensional sphere, a manifold of codimension $2$, rather than the usual $1$.
This same circle may also be formed by taking a hyperplane, whose normal direction is $u$, that is sufficiently offset from the origin, so as it slices either the sphere or the cone into that same circle.
The way I see it, this fact, that the same circle is the intersection of any two of the three geometric sets I've described, is the intuitive reason why angles are tied up with this product sum.
The hyperplane is a level set of a linear functional. That is, a hyperplane has the equation $f(x) = k$, where $f : \Bbb{R}^n \to \Bbb{R}$ is linear and $k$ is a constant. This hyperplane represents the sum product representation, as all linear functionals $f$ take the form:
$$f(x_1, \ldots, x_n) = x_1 f(e_1) + \ldots + x_n f(e_n),$$
where $e_1, \ldots, e_n$ is the standard basis. In other words, they are a dot product between your argument $(x_1, \ldots, x_n)$ and a fixed vector depending only on $f$: $(f(e_1), \ldots, f(e_n))$.
The cone is as described: it's the set of all vectors with the fixed angle $\alpha$. This represents the angle formulation of the dot product.
If we begin with a particular value for $\sum_{i=1}^n a_i x_i$, i.e. we lie on a particular plane, but we restrict our norm of $(x_1, \ldots, x_n)$ to $1$, then we lie on a cone of fixed angles. Conversely, if we begin on a cone of fixed angles, and restrict our norm to $1$ once more, then we lie on a plane, and fix our sum $\sum_{i=1}^n a_i x_i$. In this way, we see, intuitively, the connection between these two seemingly disparate definitions.