The segsize has absolutely nothing to do with the number or size of datasets. NOTHING.
Yes, a segmented or simple tablespace can have 32 datasets each of capacity 2 GB. This is automatically handled by DB2 if you use STOPGROUPS, which you definitely should be using. If you are not using STOGROUPS, you should be taken out to the woodshed. When DB2 reaches the 2GB limit, it will automatically create a new dataset. This also happens if the tablespace goes into secondary extents.
Segsize is the number of pages (from 4 to 64 in increments of 4) in a segment. Segmented tablespaces are most useful if there are multiple tables in the tablespace. Otherwise a simple tablespace (segsize 0, or omit the keyword) is fine and sometimes preferable.
For a 4K pages size with segsize equal to 64 the total bytes in the segment is 256K. Each segment has a space map to help DB2 identify freespace in that segment. Only pages for a single table are placed in any given segment (relevant only if you have more than 1 table in that tablespace).
The only thing you need to know about dataset size is that if your tablespace will exceed 64GB in length, you will need a partitioned tablespace (which will take you up to 16TB).