You don't get deals with brands on Picky; you either get selected for giveaways or not. If you want to personally approach the brands, you'll have to visit their website or social media. You have no contact with them through Picky.
Every day you log in here, write HONEST, and DETAILED reviews, interact with other's posts, you collect points. You use these points to apply for the giveaways.
To be chosen for the giveaways, you have to
1) be in a country that the brands WANT to ship to,
2) make posts on your socials, and Picky,
3) write LONG, DETAILED reviews (quality ones are not just three sentences long, stating "this is a very very good product; the packaging is so cute; nothing wrong about the product"), and lastly,
4) you have to interact with others on the app, whether it's commenting on their posts, or just upvoting them.
To summarise, you have to prove that you can provide quality, professional reviews, and that you are not here for the freebies.