Which is better structured?
"She loves to be herself instead of showing off"
"She loves being herself instead of showing off"
"She loves being and not appearing"
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She loves being herself instead of showing off.
The bolded is 5x more frequent than yours at Google Books.
She prefers being to appearing.
To Othya's comment: 'I would argue that the sentence "She prefers being to appearing." is invalid unless quotes surround the two verbs.'
It is done both ways, but mostly without, as people don't necessarily like the "power to" or "escalator" involved by the quotes. In the following, I provide the links, so one can see the printed characters (which are italics, at times).
The Early Lectures of Ralph Waldo Emerson- Volume 2 - Page 141 Ralph Waldo Emerson, Robert E. Spiller, Stephen E. Whicher - 1964 -
... who surprises him in servile occupations or coarse dress and the visiter seeing no foolish fear of him, no fear of what he may think or terror at appearances, but cheerful serenity instead falls at once into his view and prefers being to seeming.
Moderns Worth Keeping - Page 70 Russell A. Fraser -
A taxonomer like Linnaeus painting outlandish monkeys, he prefers being to thinking about it. The images that enliven his prose invite classification, and his translator, disposing them, says how some import life, others death.
D.H. Lawrence's Women in Love: A Casebook - Page 254 David Ellis - 2006
Birkin definitely prefers “being” to “having”—even having an elegant period chair or any other object of beauty. The hero of the novel is not an artist, which is meaningful.
The Absence of Myth: Dylan Thomas, Julia Kristeva, and ...- Page 166 Sophia Heller - 2012 - Preview - More editions
Tolle prefers Being to God, because Being “has the advantage that it is an open concept,” unlike the word God, which has long been closed (11).
According to VonC's answer here,
love can be followed by both an infinitive and a gerund.
I don't know what you mean by "better structured". Grammatically, all of your sentences are correct. (ignoring the
instead of mistake). If you want an opinion on what sounds better, I'd say
being herself instead of showing off
love here is meant in the sense
enjoy can only be followed by a gerund. So the gerund construct sounds more natural. But, again, that's just an opinion.