Why ⊢ for affirmative predicates and ⊨ for ¬negations?
The answer is really in the first paragraph of the quoted text, so what I'm about to attempt is really a rephrasing of that.

Remember that $\Gamma \vdash \psi$ means that there exists a formal proof of $\psi$ (in the system from $\Gamma$ blah blah blah). That is, there's some way, starting from the axioms, to syntactically manipulate the symbols according to the rules of the system to end up with $\psi$.

On the other hand, $\Gamma \models \psi$ is a statement about the semantics  of the system, i.e. the interpretation of what the symbols `mean', so $\Gamma \models \psi$ when there's no interpretation that renders all of $\Gamma$ true and $\psi$ false.

So, back to the question. When we want to show that $\Gamma \vdash \psi$ is valid, a formal proof is very nice, because it has no dependence on the meaning (semantics) of the symbols, it is simply a consequence of the rules of the system. On the other hand, if we suspect $\Gamma \vdash \psi$ is not valid, it's very hard to give a formal proof - you would have to show that every possible route to a formal proof doesn't work, i.e. that no matter what potentially-very-convoluted order you apply the rules of the system in, starting from the members of $\Gamma$, you can't get to $\psi$. Just to reiterate, you would effectively have to consider every possible proof, and show that it didn't work.

Semantic entailment kind of works the other way around. To show that $\Gamma \models \psi$ is not valid, `all' we need to find is some interpretation such that everything in $\Gamma$ is true, but $\psi$ is false - i.e. we just have to find that one counterexample. Showing that $\Gamma \models \psi$ is valid is the part that requires lots of cases - we have to show that $\psi$ holds for every interpretation for which everything in $\Gamma$ also holds.