You have stumbled upon the @formula language that is defined in the StatsModels.jl package and implemented in many statistics/econometrics related packages across the Julia ecosystem.
As you say, @formula is a macro, which transforms the expression given to it (here y ~ x1 + x2) into some other Julia expression. If you want to find out what happens when a macro gets called in Julia - which I admit can often look like magic to new (and sometimes experienced!) users - the @macroexpand macro can help you. In this case:
julia> @macroexpand @formula(y ~ x1 + x2)
:(StatsModels.Term(:y) ~ StatsModels.Term(:x1) + StatsModels.Term(:x2))
The result above is the expression constructed by the @formula macro. We see that the variables in our formula macro are transformed into StatsModels.Term objects. If we were to use StatsModels directly, we could construct this ourselves by doing:
julia> Term(:y) ~ Term(:x1) + Term(:x2)
FormulaTerm
Response:
y(unknown)
Predictors:
x1(unknown)
x2(unknown)
julia> (Term(:y) ~ Term(:x1) + Term(:x2)) == @formula(y ~ x1 + x2)
true
Now what is going on with ~, which as you say can be used for negation in Julia? What has happened here is that StatsModels has defined methods for ~ (which in Julia is and infix operator, that means essentially it is a function that can be written in between its arguments rather than having to be called with its arguments in brackets:
julia> (Term(:y) ~ Term(:x)) == ~(Term(:y), Term(:x))
true
So writing y::Term ~ x::Term is the same as calling ~(y::Term, x::Term), and this method for calling ~ with terms on the left and right hand side is defined by StatsModels (see method no. 6 below):
julia> methods(~)
# 6 methods for generic function "~":
[1] ~(x::BigInt) in Base.GMP at gmp.jl:542
[2] ~(::Missing) in Base at missing.jl:100
[3] ~(x::Bool) in Base at bool.jl:39
[4] ~(x::Union{Int128, Int16, Int32, Int64, Int8, UInt128, UInt16, UInt32, UInt64, UInt8}) in Base at int.jl:254
[5] ~(n::Integer) in Base at int.jl:138
[6] ~(lhs::Union{AbstractTerm, Tuple{Vararg{AbstractTerm,N}} where N}, rhs::Union{AbstractTerm, Tuple{Vararg{AbstractTerm,N}} where N}) in StatsModels at /home/nils/.julia/packages/StatsModels/pMxlJ/src/terms.jl:397
Note that you also find the general negation meaning here (method 3 above, which defines the behaviour for calling ~ on a boolean argument and is in Base Julia).
I agree that the GLM.jl docs maybe aren't the most comprehensive in the world, but one of the reasons for that is that the whole machinery behind @formula actually isn't a GLM.jl thing - so do check out the StatsModels docs linked above which are quite good I think.