You have two volume adjust controls on the PC (Win XP). One is for simply playing what's coming in from the port, and the other is for controlling what input is being recorded (and the volume). In the playback control panel you mute/unmute any input you don't want to come out the speakers. So you can hear multiple inputs at the same time. On the record panel you select what input you want recorded. So you can only have one active.
Even before you start recording you can unmute the line-in and adjust the volume to hear the guitar through your computer speakers. But you must use the record control panel to setup your recording.
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