Is a woman`s prayer considered invalid if non-Mahrams (marriageable men) saw her offering it?
A woman`s prayer isn`t invalidated if non-Mahrams saw her offering it, but she had better pray in isolation.
Is it permissible for a guardian (Big brother) to unlawfully stop his sister from getting married?
If the guardian denies her right in getting married for an unlawful reason, she should go to court in order to settle that matter, and the guardian is considered sinful in this case.
Is a wife considered sinful if she asked for divorce because her husband married another woman?
A second marriage is lawful, and so it is impermissible for you to ask for divorce because of that. If you are certain that you won`t be able to deliver Allah`s rights and those of your husband`s , then it is permissible for you to ask for Khul`a (Divorce on the demand of the wife). However, you should exercise patience since after difficulties, there is easiness by the will of Allah.
Is it permissible for a person who has to make up for missed fasts to fast six days of Shawwal (the month directly after Ramadan) before making up for the missed fasts?
Yes, it is permissible for him/her to do so, but it is better that they make up for missed fasts first. And Allah Knows Best.