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Mr; Mrs; Miss; Ms
makes a word more polite (usu. in fixed expressions)
state; situation; appearance; manner
「方」 has other readings with different meanings.
お客様のご注文は以上ですか。
Is that everything for your order?
田中様がお待ちです。
Mr. Tanaka is waiting for you.
山田様にはいつもお世話になっております。
We are always grateful for Mr. Yamada's support.