Firstly yes: Go "My Computer" when the iPhone is attached and you'll see it listed. Double clcik and you'll see all your photo's. This is the only thing you can ever browse to on an un-jailbroken phone. Then just copy and paste to your chosen Pc folder.
Secondly Yes: All you have to do is set up a Folder, say within "My Photos/Pictures", name it something easy like iPhone. Within that set new folders and name then say, Cars, family etc and copy the photos from thier original folders and place a copy in the new folder you wish to sync
Then go to itunes and with the iphone attached, go to your iPhone (Halfway down left panel under Devices)
Then click PHOTOS tab and click the Grey box and select "Choose Folder" then browse to the "iPhone" folder you set up earlier.
Then in that iPhone folder bung any photo's you wish, add sub folders if you like too labeled say, "Family" "cars" as mentioned above.
Job done, photo's will now sync with that folder everytime you connect and upload your photos' in that folder to the iPhone

Hope this helps