Edit: A gentle book for character theory is G. James and M. Liebeck's Representations and Characters of Groups. Its chapter 23 is entirely to devoted to all of these different ideas (as well as Frobenius's original motivation) without using anything fancy. It has many examples, many exercises, and solutions to many exercises. I think it is useful for both group theorists and people who just want to use representations.

For fancier things: I. Reiner's Maximal Orders has nice coverage of the division algebras associated to finite group algebras (and their maximal orders). My favorite textbook treatment of the numerical invariant of the division algebras are Albert's Modern Higher Algebra and Structure of Algebras, but some people think they are old fashioned. Recent treatments will often get lost in technicalities that are irrelevant to group algebras. You might be OK with one of large textbooks on algebra; many have a chapter on Central Simple Algebras and the Brauer Group. MathOverflow readers will probably like Rowen's Algebra: A Non-commutative View.

You asked a lot about the F–S indicator. I'll answer part of it for now, so that there is a smaller piece to answer later.

Your first division algebra question makes more sense in a slightly different context: if T is an irreducible real representation of G (an irreducible ℝG-module), then three cases occur: End_ℝG(T) = ℝ is real, = ℂ is complex, or = ℍ is quaternionic. In the first case T is also irreducible over the complexes and its Schur indicator is +1. In the second case T is not irreducible over the complexes, but is instead the sum of two complex conjugate representations, both of whose Schur indicators are 0. In the third case, the representation "ramifies" when extended to the complexes, and you get the sum of two isomorphic representations (both of) whose Schur indicator is -1.

I like to think of this in terms of complex endomorphism rings, but then it no longer specifically mentions the quaternions: End_ℂG(T) = ℂ is complex when the Schur indicator is +1, = ℂ×ℂ when the Schur indicator (of the summands) is +0, = M₂(ℂ) when the Schur indicator (of the summand) is -1. These correspond to applying –⊗_ℝℂ to the reals, complexes, and quaternions.

Your numerical invariant of the division algebra is probably best understood as a quest for the "Brauer group" of F. There is a very well-defined and reasonably well-understood theory for this. It is usually phrased in terms of "central simple algebras", but it turns out to mostly be a matter of notation. For F a p-adic field, then yes, you mostly just get a number, but for a general field it is a little bit of a stretch (but not insane) to say you get a number.

You asked a lot about the F–S indicator. I'll answer part of it for now, so that there is a smaller piece to answer later.

Your first division algebra question makes more sense in a slightly different context: if T is an irreducible real representation of G (an irreducible ℝG-module), then three cases occur: End_ℝG(T) = ℝ is real, = ℂ is complex, or = ℍ is quaternionic. In the first case T is also irreducible over the complexes and its Schur indicator is +1. In the second case T is not irreducible over the complexes, but is instead the sum of two complex conjugate representations, both of whose Schur indicators are 0. In the third case, the representation "ramifies" when extended to the complexes, and you get the sum of two isomorphic representations (both of) whose Schur indicator is -1.

I like to think of this in terms of complex endomorphism rings, but then it no longer specifically mentions the quaternions: End_ℂG(T) = ℂ is complex when the Schur indicator is +1, = ℂ×ℂ when the Schur indicator (of the summands) is +0, = M₂(ℂ) when the Schur indicator (of the summand) is -1. These correspond to applying –⊗_ℝℂ to the reals, complexes, and quaternions.

Your numerical invariant of the division algebra is probably best understood as a quest for the "Brauer group" of F. There is a very well-defined and reasonably well-understood theory for this. That is usually phrased in terms of "central simple algebras", but it turns out to mostly be a matter of notation. For F a p-adic field, then yes, you mostly just get a number, but for a general field it is a little bit of a stretch (but not insane) to say you get a number.

On the off chance someone is interested, this is one of the places where the Schur index is easily understood. If the Schur indicator is +1, then the field of values and the splitting field are equal to the reals. If the Schur indicator is 0, then the field of values and the splitting field are equal to the complexes. If the Schur indicator is -1, then the field of values is the reals, but the splitting field is degree 2 (the complexes), so the Schur index is 2. This is also the smallest multiple of the character that has a representation realizable over the field of values, and so this is is why in the -1 case, T splits into two (self-conjugate) copies of itself. In terms of blocks of the group ring, this block is a matrix ring over the quaternion algebra, and it contains many copies of the irreducible. Each copy of the irreducible has a centralizer isomorphic to the complexes, a splitting field of the block and the irreducible.