Pretty new to the forum and a little paranoid/suspicious about how the marketplace section works. (I eventually will be trying to sell an unused 650w PSU)
What's the best way to ensure a transaction occurs honestly? Using an escrow service? Or just being very selective with who you're working with (ie checking references, etc)
If you are selling, generally the buyer is the one taking the risk when paying before shipment.
If the buyer sends bitcoins to you then there's really no risk to you (though some nutjob might try to claim you shipped an empty box and shame you to cough up some money, etc.)
The #bitcoin-escrow IRC channel along with ratings from the #bitcoin-otc Web of Trust (WoT) is probably the best place currently to find a trusted escrow that you can hire:
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http://webchat.freenode.net/?channels=#bitcoin-escrow -
http://wiki.bitcoin-otc.com/wiki/OTC_Rating_SystemThere is good information here:
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http://wiki.bitcoin-otc.com/wiki/Using_bitcoin-otc#Safety:_avoiding_fraud