Hecate, her title, and her role has a deeper meaning that just the words.
First let us examine her name. The origin of her name seems to be the goddess Hecate of the underworld of Greek mythology.
Originally she was a matron god related to witchcraft and the moon, whose appearances have changed with time, she has been depicted as mistress of witchcraft with three faces, a girl, and a mature woman, an elderly woman, and a three-way road.
In Volume SIII of the light novel series, its revealed that she went by another name in the past, "Nüwa" (女媧). Nüwa is the matron goddess of Chinese mythology, who created humans. The myth
女娲补天 recounts her mending the heavens after one of the pillars holding up the sky and breaking the rope the connected the earth and sky, tilting the direction the sun and moon moved in the sky and changing the direction the rivers causing them to flow towards the ocean on earth. In the myth, she is described as having the body of a snake, a human head, and the virtue of a divine being, carrying a builder's compass in one hand.
Now lets get back to the title at hand, 頂の座. 頂 refers to the highest point overhead. 座 here likely refers to star constellations, as in 星座. In other words can refer to the highest overhead constellations, given her divine origins associated with the sky. Likely in reference to her high authority amongst the Crimson Denizens. Additionally, her most powerful Unrestricted Spell is called Aster, which means Star in Greek. Marjorie Daw also refers to her as, 星の王女様, Princess of the Stars. The throne room of the Seireiden also has a starry atmosphere.
But that's not all. 座 here likely has refers to a pedestal to sit on. Not just any pedestal, but one fit for a heavenly being, which may refer to traditional sacred Shinto dances former refered to as 神座 (kamukura or kamikura). The distinction here is that shrine maidens, through sacred dance, become vessels to convey the will of God. The distinction with Hecate is that the title may also refer to her as "the highest seat of god", referring to her role as Priestess. After all she is the Priestess/Shrine Maiden to the Snake of the Festival, 祭礼の蛇, the Creator God of the Crimson Denizens. Therefore title also refers to here status as top ranking representative (i. e., High Priestess) of the Crimson Denizens.