Can you unstake them at any time?
I don't know about staking on exchanges, but watch out for coins like ATOM, DOT, and probably some others that have unstaking periods (which I've heard the rationale for and still think are ridiculous). Also, if you can stake a coin using your own wallet and having custody of your own private keys, do that and don't use an exchange. You've been around long enough to know that, even if we're talking about exchanges with decent reputations and strong regulations like Coinbase and Gemini.
Are there any safe places to stake btc, eth and those top coins?
Don't you know you can't stake
BTC by now? Sure, there are places you can use for lending and such, but it's not a PoS coin.