Ok Solo mining is the process of mining alone. When you connect to a pool, what technically happens is that all miners are connected to the same bitcoin-client in order to confirm transactions. This increases the probability of "finding" a block, but in turn the block reward is shared among all miners.
When you solo mine you connect your miner to your own local bitcoin client and try to "find" a block on your own. The probability of that is a lot lower but in turn you do not share the block reward.
Given how the bitcoin network works however. In the long run (that means if you mine either way VERE VERY LONG) solo mining and pooled mining will get you exactly the same amount.
In realistic timeframes though pooled mining definetly is the better way if your hardware has only small hashrate. A wild guess here is that it would take more than severeal tens of TH/s (that is Terrahashes per second, which is 1000 GH/s) to get more out of solo mining than pooled mining.
In the range that most current hardware can deliver solo mining is more like playing the lottery. But what is true is: If you are lucky you can cash out big time.
What you need n order to solo mine on windows is: Bitcoin-Core client, Mining hardware and BFGMiner or CGMiner.
Install Bitcoin-core, start it and let it download the whole blockchain (about 20 GB as of now).
Use a text editor to create a bitcoin.conf file C:\User\yourusername\AppData\Roaming\Bitcoin\
Put the following lines in bitcoin.conf:
server=1
rpcuser=username
rpcpassword=password
rpcallowip=127.0.0.1
rpcport=8332
Then use 127.0.0.1:8332 as the server and the username and password you chose as the credentials to connect BFGMiner or CGMiner to the Bitcoin_Core client and have it mine.
Note: if you have other pools in the list of your miner software it might throw errors, try removing all pools from the list but your local connection.
The output for BFGMiner will also be different. You will not see any "share accepted" lines. To see if it works see if the effective average hashrate of your hardware changes to the same value and see if the BS (best Share) value in the upper right changes at the start.