I personally, even after handling Bitcoin for years triple check my transactions before sending them, since the only real safety net you have is the confirmation window that your wallet software usually spits out, asking you to confirm you want to send x amount to x address. Getting complacent here could mean you misplace a decimal point, which is much easier than with fiat, because you are usually dealing with decimal points more regularly, due to prices not being tied to values such as $9.99. Instead, its something like 0.00057 which can be easily mistaken.
Also, whenever you are dealing with someone person to person, and you don't actually know them, or have enough trust of them , you need to be seeking out alternative ways to protect both parties from loss of coins. Basically, always use some sort of escrow, and by that I mean a trusted escrow, or even better a multi sig system.
By escrow, you mean entrusting your funds to a third-party? If that's the case, you'll add another risk. Instead of doing that, you can do a 2-of-3 multi-sig with a neutral third-party (basically an escrow but with a different mechanism).
From my observations, this isn't used nearly as much as it should be. I honestly, thought this would have become a standard within the industry by now, and I do understand it has its caveats, especially on time sensitive matters, but its by far one of the better ways of dealing with an escrow. I don't like that some P2P exchanges, still insist on using that site as an escrow, basically eliminating the very purpose of using a P2P exchange. 
