This rare kanji has no clear standalone meaning. Treat its meaning as uncertain.
娰 combines 女 (woman) with 似 (resemble). The exact historical development is uncertain, but it likely relates to a woman's name or a resemblance concept.
A woman 女 beside 似 (resemble) suggests a woman who resembles someone, but the exact meaning is unclear.
For シ, imagine a woman named Shi who resembles her sister: Shi -> シ.