Nope, and nope.
Family Sharing is an all-or-nothing deal in every regard. The other party will have access to your full library - at least the games that are eligible to be shared, which will be most of them - and you can't access the library at the same time, even if you're playing separate games.
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+1 Also the main account holder always has priority. So if your sibling is playing game A, and you want to play game B, then you can just launch game B and play. The sibling playing game A will get a notification saying that they have 5 minutes to save and exit, or else it'll autoquit.
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Try with this: http://store.steampowered.com/parental/set
I'm not sure how it works, but you can select which game will be playable (no idea if this apply only on your account or family sharing, it's in the same menu in steam settings).
About the second thing, nnnope, no matters what are you both playing. If the library owner opens a game, your friend have 5 extra minutes to play (to save the game and stuff)
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So I want to share my games but I want to block access to my main games. Anyway I can do that? While more then 1 person can use the library so if they want to play a random game I'm not playing they can.
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