i have absolutely NO IDEA weather or not this nas device supports it.
AFAIK the partition will not magically expand if you do that.
I have no idea what the linksys nas200 supports...
Lets say the nas drives are Drive A and Drive B, and that the new drives are C and D.
To answer the question the way you ASKED it: if the NAS has an option to select a drive to mirror unto the other, then perhaps you can do it this way:
take out drive A from the nas, put it in a PC, put drive C in that PC as well. mirror drive A to drive C, expand the partition from 250GB to whatever TB drive C has. take out drive B from the nas, place the drive C into the NAS and set it as "good"
Put the unformatted Drive D into the NAS and have the NAS mirror the data from drive C to Drive D...
But the easy simple and surefire way to do it is:
take out Drives A from the NAS, make sure your PC can read it... if it can take drive B out of the nas and put it aside (in case of catastrophic failure). If the PC can NOT read drive A that put it back in the NAS to avoid losing data.
Put Drive C and D into the NAS... set up a new mirror array and format them...
Plug Drive A or B into a PC on the same network as the nas, and then simply copy all the files from drive B (on PC) to the new NAS array.