Chance to dodge attacks and chance to evade.

Spells have no accuracy - evasion has no way to interact with them.
They can be dodged by Phase Acrobatics, but never evaded.

Each of the three defenses has a weakness; Armour only protects against physical damage, Evasion only protects against attacks, and Energy Shield is ignored by Chaos damage.
There are no "attack based spells"

Skills which use your weapon for damage are attacks, not spells. Cleave, Burning Arrow, Elemental Hit, etc are all attacks, which have accuracy which is checked against the opponent's evasion.

Spells are skills that are not attacks, such as Cold Snap, Ice Spear, or the curses. They don't deal weapon-based damage and have no accuracy. Spells cannot be evaded.
The spell and attack distinction will probably be made more explicitly visible on skill gems in a future update to how items are displayed.
By default, blocking only works against attacks.
There is a stat which will make a percentage of your block chance work against spell damage as well - it's present on some unique items, I'm not sure if it's available anywhere else at the moment.
Yes, Rhoas use shield charge.

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