You can have multiple instruments connected and working at the same time on the same PC. However, if you are using GPIB, although you communicate to the instruments in parallel, they will not communicate simultaneously. It will be nearly at the same time. So you can't use the PC to trigger the start of an acquisition and have them start at the very same time. There are tricks you can do on some instruments, but let's not go into that...
Now it also depends on your definition of "at the same time"... If you allow 4 to 100 ms delay between the two, then yes, you should be able to accomplish that. However, you will have to be careful of Query commands or when reading data back from an instrument.
R