Penny raised an interesting point in this thread about user friendly issues about e-commerce packages:
One of the easiest systems to use that I've seen are the eSHOP packages from 1&1
It very much depends on the scale you want to pitch at. You say money is not an issue and that's all well and good, butmost of the good mainstream commerce software solutions that allow you to build your commerce site localy with a user friendly interface cost many hundreds and have limitations of their own.
What is it you want to sell ?
Will you have a large product range and will those products have lots of possible sub-categories ?
Do you have web hosting arranged yet and if not would you prefer Windows or Linux hosting ?
There are so many questions to ask which would help me or anyone else to answer yours. Most of the off-the-peg solutions not only cost quite a lot but they work best in particular environments where a very large product range is the norm. Small scale solutions that work well are not as common as you would like them to be.
Try and give as much detail as possible about how you would like to trade and the range of goods you plan to offer. You needn't get too specific, but the more information you give, the better the potential advice will be.