I've had experience with both. And for a while was using both. That in itself can be a problem in that many bookies, and Pinnacle is one, insist on you withdrawing to whichever they deem you deposited with. It became extremely tricky working out where I had to withdraw to and how much before I could use the other which I had reason to prefer.
In the end I sacked Neteller and have since used Moneybookers exclusively. Primarily because Moneybookers were quicker with withdrawals and pay clear funds into my bank account whereas Neteller used "wires" which for some reason resulted in my bank charging a fee and putting a hold on clearance.
I got VIP status at Moneybookers and they are forever running cash back promotions which I enjoy. Never had any real issues using them. A strong recommendation is to insist on getting a security token from them which makes is near impossible for a hacker to get into your account.
I used Moneybookers for a while, but had a problem with them over a password. I withdrew some money from a bookie and tried to log into my Moneybookers account to find it locked. When I asked why it was locked (which it hadn't been the previous week) I was told it was for security purposes because I had not recently changed my password. I had not been warned that it was necessary to change my password to avoid the account being locked. The only way I could get my account unlocked was to privide ID. I sent ID, which was rejected because the resolution was not good enough, and they pointed me to a page to upload a scan of my passport, which had to be in colour. When I tried to upload the scan I found that the page would not accept an upload of a file of the required size, and when I reduced the size it was again not clear enough. Eventually I managed to email them an acceptable scan, and they did unlock my account. The whole process took about a week and was worrying as I had nearly £3000 in there. I promptly removed most of it and have hardly used Moneybookers since.
I am aware that other people have had no problems at all with Moneybookers, and it does seem to be the preferred e-wallet to use with bookies. However I found them difficult to deal with and totally unsympathetic to my problem, to which they would only respond that it was for my own good and unless I could provide acceptable ID I would not get my money back. My account had been verified when I opened it so I was rather surprised to be asked for further ID from them. On the plus side I never had any issues with transactions to and from bookies using Moneybookers, and withdrawals from bookies (mainly Bet24 and Jenningsbet) usually arrived very quickly.
Well here first I have to say that I'm an exception as I am a Turkish citizen who tries to find the optimum method as we have strict legislation about betting. I think Neteller is faster and simple. In moneybookers it takes too long to transfer money from your Skrill account to your bank account . On the other hand Neteller's master card is open for use in any bank ATM. When you use MB you can transfer the money to your bank account and withdraw from the bank (unlimited) with your ID ,tough you can only use Neteller card at atms where you have daily withdrawal limits which can be the only negative skill of NEtller.