To get all spells, you need to find 2 mages sage frake and witch yuria, then you can get all the spells by those 2 mages most of the spells need demon boss souls to get them.
First sage frake
World 3-1 (Tower of Latria) - Locked in a cell.
Nexus (Unlockable) - After you free him from his cell in 3-1. To unlock him:
Get the Special Key from the top of the tower located right before the 3-1 Boss' area. It hangs on the wall behind the Dregling. you must kill to defeat the boss.
Return to Freke's cell and unlock it.
Talk to him; you will receive Geri's Stiletto.
When you return to the Nexus, he will appear near his apprentice.
Second witch yuria ( you need to rescue her).
go to world 1-3
Obtain Iron ring of keys and Official's Cap by killing the two Fat Officials in 1-3.
Backtrack to the end area of 1-2 just before the Tower Knight boss fog. In the room with stairs going up into the tower, there is a door which can be unlocked using the Iron ring of keys.
This leads down to a dungeon below. Defeat the Fat Official down there to obtain the Bloody Key and open the cells to rescue Biorr.
Go back to the beginning of 1-3, the Bloody Key will unlock the gate in the right alleyway behind the dog carts and fountain.
Follow the alleys, and eventually the player will arrive at a tower, where on the top floor there is a raised staircase and a watching Fat Official above.
Equip the Official's Cap as a disguise and the staircase will be lowered.
Defeat the Fat Official (he will not be hostile until you attack him or remove the hat).
Unequip the Official's Cap and speak to Yuria to finish the rescue.
Here is a list from all the spells you need
Soul Arrow: Freke`s Apperntice or sage Frake: 1000 souls.
Flame Toss: Freke`s Apprentice or sage Frake: 1000 souls.
Protection: Freke`s Apprentice or sage Frake: 5000 souls.
Enchant Weapon: Freke`s Apprentice sage Frake: 5000 souls.
Demon`s Prank: Freke`s Apprentice or sage Frake: 500 souls.
Water Veil: Freke`s Apprentice or sage Frake: 500 souls.
Cloak: Freke`s Apprentice or sage Frake: 500 souls.
Warding: Sage Freke: Iron Demon's Soul (Tower Knight).
Soul Ray: Sage Freke: Doll Demon's Soul (Fool`s Idol).
Homing Soul Arrow: Sage Freke: Yellow Demon's Soul (Old Monk).
Firespray : Sage Freke: Hard Demon's Soul (Armor Spider).
Fireball: Sage Freke: Dragon Demon's Soul (Dragon God).
Light Weapon : Sage Freke: Silver Demon's Soul (Penetrator).
Acid Cloud: Sage Freke: Eroded Demon's Soul (Dirty Colossus).
Poison Cloud: Sage Freke Wriggling Demon's Soul (Leechmonguer).
Death Cloud: Sage Freke: Pureblood Demon's Soul (Maiden Astraea).
Firestorm: Yuria the Witch: Dragon Demon's Soul (Dragon God).
Ignite: Yuria the Witch: Hard Demon's Soul (Armor Spider).
Curse Weapon: Yuria the Witch: Silver Demon's Soul (Penetrator).
Thirst: Yuria the Witch: Yellow Demon's Soul (Old Monk).
Relief: Yuria the Witch: Pureblood Demon's Soul (Maiden Astraea).
Soulsucker: Yuria the Witch: Maiden In Black's Demon's Soul (Maiden in Black).
Good luck :)