I had a similar problem and resolved this just now (Rockbox 3.13). In my case it was a wrong partition type in the partition table. It is very important that the microSD FAT32 partition is marked as 0x0B (FAT32)!
On Linux you can use cfdisk /dev/sdX, where X is the drive letter for your card, then delete all partitions (that you want to delete anyway, don't know how Rockbox deals with more than one partition), create a new primary one and use "b" as type. Write to disk, format with mkdosfs -F32 /dev/sdX1 (assuming it's the first partition) and my card got detected (I had it marked as NTFS by accident). I'm sure you can find partitioning (this part is important and separate from formatting) and formatting tools on Windows as well.
Edit: Of course you should check all the usual stuff too: Card works at all, card works on standard firmware, card is exposed on Rockbox via USB to your PC....