In the 'simplewallet' window, type 'transfer w x y z' , without the ' '
w = the number of transactions you would like yours to be indistinguishable from. called the 'mixin' count. Higher numbers = higher fees and larger size of transaction in bytes. 1-3 seems pretty good. 0 if you'd like to only have a stealth address.
x = the address you want to send to (longer string)
y = the actual amount you want to send
z = the transaction id. this is used so that exchanges can track who is who because they use one wallet to collect all incoming transfers. it is shorter than the wallet address. this is not required, and can be left blank for regular transactions. It is required for sending to an exchange though (or any shared wallet that's technically not just yours)
If you would like to solo mine, yes all machines must be synchronized and running the daemon.
If you would like to pool mine, you can go to any of the pool pages listed in the original post and download the software and follow the instructions on how to set it up on that pool site. Please consider a pool built from source provided by zone117x (I think Wolf0 and mindless just opened one). You will not need the daemon running or synchronized for pool mining. In fact, you won't even need simplewallet or monero software at all (besides the mining program) on every single mining computer. Just need an address to mine to .. so one computer.