Setup a deduplication device for the backup to NAS.
Setup one backup with all targets selected and multistream and multiplex enabled. With LTO4 try out 5 streams for the multiplex. It will be necessary to try different setting to find the optimum setting.
Job Engine buffers can be adjusted as well (under Server Admin Config) but there too trial and error is the only way to know what will be best.
If a buffer is too large the job has to wait for it to fill, if it is too small then the data gets sent too fast.
Keep that large volume deframented, fragmentation can really degrade throughput on large volumes with many small files.
Also if that large volume is running under Windows 2008 R2 install this storport.sys update.
http://support.microsoft.com/kb/981208
Adjusting the Windows Client Agent backup priority might help as well.
It think the CA support site has a tech doc on Client Agent registry setting that can help with performance as well.